Production method for water-absorbing resin powder

ABSTRACT

[PROBLEM] 
     It is an object of the present invention to enhance and stabilize properties of a water-absorbing resin, for example, damage resistance or water-absorbing speed, by a simple and convenient method without requiring change of raw materials or expensive facility investment, in a large scale production method for the water-absorbing resin. 
     [MEANS FOR SOLVING THE PROBLEM] 
     It is solved by circulation of the water-absorbing resin in a predetermined amount or more in the pulverization step before the surface cross-linking step. That is, at least a part of the classified polymer is supplied again to the same or different pulverization step, before the surface cross-linking step, wherein circulation pulverization ratio in the pulverization step, represented by the following equation is larger than 1.50: 
       (Circulation pulverization ratio)=(total supply amount of the water-absorbing resin to the pulverization step)/(total discharge amount of the water-absorbing resin at the drying step) 
     (wherein total supply amount of the water-absorbing resin to the pulverization step)=(total discharge amount of the water-absorbing resin at the drying step)+(amount of the classified polymer supplied again to the same or different pulverization step)).

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to a production method for water-absorbingresin powder, and in more detail, the present invention relates to aproduction method for obtaining water-absorbing resin powder having highliquid permeability under highly pressurized condition, by performingsurface cross-linking.

2. Background Art

The water-absorbing resin (Super Absorbent Polymer; SAP) is awater-swelling and water-insoluble polymer gelling agent, and is widelyused mainly in disposable applications as absorbent articles such asdisposable diapers, sanitary napkins; water-retention agent foragriculture and gardening; water-stops for industrial use; and the like.As a raw material of such a water-absorbing resin, many monomers orhydrophilic polymers have been proposed. In particular, a polyacrylicacid (salt)-type water-absorbing resin using acrylic acid and/or a saltthereof as a monomer, is produced most industrially from the viewpointof high water absorbing performance thereof.

Such a water-absorbing resin is produced via a polymerization step, adrying step, (a removing step of a non-dried substance, as needed), apulverization step, a classification step, a surface cross-linking stepand the like (PATENT LITERATURES 1 to 5). With shift to higherperformance of disposable diapers, which are main applications, manyfunctions have been required also for the water-absorbing resin.Specifically, not only simple high absorption capacity but also manyproperties have been required for the water-absorbing resin, such as gelstrength, water-soluble amount, water-absorbing speed, absorbencyagainst pressure, liquid permeability, particle size distribution, urineresistance, antibacterial, impact resistance, powder fluidity,deodorant, coloring resistance, and low powder dust. Therefore, manyproposals have been made, such as many surface cross-linkingtechnologies, additives, and changes of production steps, in literaturesother than the above or the following PATENT LITERATURES 1 to 49.

Among the above properties, in recent years, liquid permeability hasbeen seen as a more important factor with increase in use amount (forexample, 50% by weight or more) of the water-absorbing resin in thedisposable diapers. And, many improvement methods or modifiedtechnologies of liquid permeability under load or liquid permeabilitywithout load have been proposed, such as SFC (Saline FlowConductivity/PATENT LITERATURE 6) or GBP (Gel Bed Permeability/PATENTLITERATURES 7 to 9).

In addition, in such properties described in the above, manycombinations of a plurality of parameters including liquid permeabilityhave also been proposed, and there have been known technology forspecifying impact resistance (FI) (PATENT LITERATURE 10), technology forspecifying water-absorbing speed (FSR/Vortex) and the like (PATENTLITERATURE 11), and technology for specifying a product of liquiddiffusion performance (SFC) and core absorbing amount after 60 minutes(DA60) (PATENT LITERATURE 12).

Further, as a method for enhancing liquid permeability such as SFC orGBP, there have been known technology for adding gypsum beforepolymerization or during polymerization (PATENT LITERATURE 13),technology for adding a spacer (PATENT LITERATURE 14), technology forusing 5 to 17 mole/kg of a nitrogen-containing polymer having a nitrogenatom capable of protonation (PATENT LITERATURE 15), technology for usingpolyamine and a polyvalent metal ion or a polyvalent anion (PATENTLITERATURE 16), technology for coating the water-absorbing resin havinga pH below 6 with polyamine (PATENT LITERATURE 17), and technology forusing poly ammonium carbonate (PATENT LITERATURE 18). Other than these,there have also been known technology for using polyamine in a solubleamount of 3% or more, and technology for specifying wicking index (WI)or gel strength (PATENT LITERATURES 19 to 21). In addition, there hasalso been known technology for using a polyvalent metal salt, as well ascontrolling a methoxy phenol, which is a polymerization inhibitor inpolymerization, to improve coloring and liquid permeability (PATENTLITERATURES 22 and 23). Still more, technology for controlling a bulkspecific gravity at a high level by grinding the particles (PATENTLITERATURE 24) has also been known.

In addition, in addition to liquid permeability, water-absorbing speedis also an important fundamental property of the water-absorbing resin,and as a method for enhancing such water-absorbing speed, technology forenhancing water-absorbing speed by enhancing specific surface area hasbeen known. Specifically, there have been proposed technology forcontrolling a particle diameter finely (PATENT LITERATURE 25),technology for granulating fine particles with large surface area(PATENT LITERATURES 26 to 28), technology for making a porous substanceby freeze drying hydrogel (PATENT LITERATURE 29), technology for surfacecross-linking of particles at the same time as granulation (PATENTLITERATURES 30 to 32), technology for performing foaming polymerization(PATENT LITERATURES 33 to 48), and technology for foaming andcross-linking after polymerization (PATENT LITERATURE 49) and the like.

In the above foaming polymerization, as a foaming agent to be used in amonomer, specifically there have been known technology for using acarbonate salt (PATENT LITERATURES 33 to 40), technology for using anorganic solvent (PATENT LITERATURES 41, and 42), technology for using aninert gas (PATENT LITERATURES 43 to 45), technology for using an azocompound (PATENT LITERATURES 46 and 47), and technology for using aninsoluble inorganic powder (PATENT LITERATURES 48) and the like.

PRIOR ART LITERATURES Patent Literatures

-   PATENT LITERATURE 1: U.S. Pat. No. 6,576,713 specification-   PATENT LITERATURE 2: U.S. Pat. No. 6,817,557 specification-   PATENT LITERATURE 3: U.S. Pat. No. 6,291,636 specification-   PATENT LITERATURE 4: U.S. Pat. No. 6,641,064 specification-   PATENT LITERATURE 5: US-A-2008/0287631 specification-   PATENT LITERATURE 6: U.S. Pat. No. 5,562,646 specification-   PATENT LITERATURE 7: US-A-2005/0256469 specification-   PATENT LITERATURE 8: U.S. Pat. No. 7,169,843 specification-   PATENT LITERATURE 9: U.S. Pat. No. 7,173,086 specification-   PATENT LITERATURE 10: U.S. Pat. No. 6,414,214 specification-   PATENT LITERATURE 11: U.S. Pat. No. 6,849,665 specification-   PATENT LITERATURE 12: US-A-2008/125533 specification-   PATENT LITERATURE 13: US-A-2007/293617 specification-   PATENT LITERATURE 14: US-A-2002/0128618 specification-   PATENT LITERATURE 15: US-A-2005/0245684 specification-   PATENT LITERATURE 16: WO 2006/082197 pamphlet-   PATENT LITERATURE 17: WO 2006/082188 pamphlet-   PATENT LITERATURE 18: WO 2006/082189 pamphlet-   PATENT LITERATURE 19: WO 2008/025652 pamphlet-   PATENT LITERATURE 20: WO 2008/025656 pamphlet-   PATENT LITERATURE 21: WO 2008/025655 pamphlet-   PATENT LITERATURE 22: WO 2008/092843 pamphlet-   PATENT LITERATURE 23: WO 2008/092842 pamphlet-   PATENT LITERATURE 24: U.S. Pat. No. 6,562,879 specification-   PATENT LITERATURE 25: U.S. Pat. No. 5,505,718 specification-   PATENT LITERATURE 26: US-A-2007/015860 specification-   PATENT LITERATURE 27: WO 2005/012406 pamphlet-   PATENT LITERATURE 28: U.S. Pat. No. 5,002,986 specification-   PATENT LITERATURE 29: U.S. Pat. No. 6,939,914 specification-   PATENT LITERATURE 30: U.S. Pat. No. 5,124,188 specification-   PATENT LITERATURE 31: EP No. 0595803 specification-   PATENT LITERATURE 32: EP No. 0450922 specification-   PATENT LITERATURE 33: U.S. Pat. No. 5,118,719 specification-   PATENT LITERATURE 34: U.S. Pat. No. 5,154,713 specification-   PATENT LITERATURE 35: U.S. Pat. No. 5,314,420 specification-   PATENT LITERATURE 36: U.S. Pat. No. 5,399,591 specification-   PATENT LITERATURE 37: U.S. Pat. No. 5,451,613 specification-   PATENT LITERATURE 38: U.S. Pat. No. 5,462,972 specification-   PATENT LITERATURE 39: WO 95/02002 pamphlet-   PATENT LITERATURE 40: WO 2005/063313 pamphlet-   PATENT LITERATURE 41: WO 94/022502 pamphlet-   PATENT LITERATURE 42: U.S. Pat. No. 4,703,067 specification-   PATENT LITERATURE 43: WO 97/017397 pamphlet-   PATENT LITERATURE 44: WO 00/052087 pamphlet-   PATENT LITERATURE 45: U.S. Pat. No. 6,107,358 specification-   PATENT LITERATURE 46: U.S. Pat. No. 5,856,370 specification-   PATENT LITERATURE 47: U.S. Pat. No. 5,985,944 specification-   PATENT LITERATURE 48: WO 2009/062902 pamphlet-   PATENT LITERATURE 49: EP No. 1521601 specification

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

-   As described above, to enhance properties of the water-absorbing    resin, proposals have been made, such as many surface cross-linking    technologies, additives, and changes of production steps. Among    them, liquid permeability (PATENT LITERATURES 6 to 24) or    water-absorbing speed (PATENT LITERATURES 25 to 49) is important as    a fundamental properties of the water-absorbing resin, and many    improvement technologies have been proposed.

However, the change or the addition of raw materials of thewater-absorbing resin, such as a surface cross-linking agent or anadditive (polyamine polymer, inorganic fine particles, thermoplasticpolymers) or the like, resulted in not only decrease in safety of rawmaterials or cost-up but also decrease in other properties, in somecases. In addition, the addition of a new production step not onlycauses cost-up due to expensive facility investment or energy thereofbut also requires an industrially complicated operation, and rathercauses decrease in productivity or properties in some cases.

In addition, the above method showed a certain degree of effect in asmall scale such as in an experiment room, however, showed in some casesnot sufficient effect in a large scale in a practical plant (forexample, in a production amount of 1 [t/hr] or more).

Accordingly, to improve the above problem, it is an object of thepresent invention to provide a method for enhancing and stabilizingproperties (for example, liquid permeability or damage resistance) of awater-absorbing resin, by a simple and convenient method withoutrequiring change of raw materials or expensive facility investment, in alarge scale production.

Means for Solving the Problem

To solve the above-described problem, the present inventors have focusedattention on a pulverization step of the water-absorbing resin, whichhas conventionally been never paid any attention as an improvementmethod for the above liquid permeability or water-absorbing speed, andfound, that liquid permeability or damage resistance of thewater-absorbing resin can be enhanced (even when compared at the sameparticle size), by circulating predetermined amount or more, and havethus completed the present invention.

That is, the method for producing the water-absorbing resin according toone aspect of the present invention is:

a method for producing water-absorbing resin powder, sequentiallycomprising:a polymerization step for polymerizing an aqueous solution of acrylicacid (salt) to obtain a hydrogel-like cross-linked polymer;a drying step for drying the obtained hydrogel-like cross-linked polymerto obtain a dried polymer;a pulverization step for pulverizing the obtained dried polymer with apulverizing means to obtain a pulverized polymer;a classification step for classifying the obtained pulverized polymer toobtain a classified polymer; anda surface cross-linking step for surface cross-linking the obtainedclassified polymer. And, at least a part of the classified polymer issupplied again to the same or different pulverization step, before thesurface cross-linking step. In addition, it is also characterized inthat, in this case, circulation pulverization ratio in the pulverizationstep, represented by the following equation:

(Circulation pulverization ratio)=(total supply amount of thewater-absorbing resin to the pulverization step)/(total discharge amountof the water-absorbing resin at the drying step)  [EXPRESSION 1]

is larger than 1.50, wherein (total supply amount of the water-absorbingresin to the pulverization step)=(total discharge amount of thewater-absorbing resin at the drying step)+(amount of the classifiedpolymer supplied again to the same or different pulverization step).

Advantageous Effect of the Invention

The present invention is capable of enhancing and stabilizing liquidpermeability or damage resistance of the water-absorbing resin, by asimple and convenient method of controlling a circulation pulverizationratio at the pulverization step before the surface cross-linking step,without requiring change of raw materials or expensive facilityinvestment.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic drawing showing a flow of supplying again apulverized polymer to the same pulverization step after classification.It is a schematic drawing showing the flow where a classification stepis set after the pulverization step for a dried substance (the wholeamount), for classifying to “objective particle size (for example, 850to 150 μm)”/a non-passed through substance/fine powder, at saidclassification step, and circulating only the non-passed throughsubstance to the pulverization step. It should be noted that, althoughnot shown in Figures, the dried substance may be crushed as neededbefore the pulverization step.

FIG. 2 is a schematic drawing showing a flow of supplying again apulverized polymer to a different pulverization step (a secondpulverization step) after classification. In the conceptual diagram ofFIG. 1, after supplying only the non-passed through substance to asecond pulverization step, it is classified again at the secondpulverization step to “objective particle size (for example, 850 to 150μm)”/a non-passed through substance/fine powder; only the non-passedthrough substance is supplied to the pulverization step (the secondpulverization step); and the non-passed through substance at the secondclassification step is supplied as needed to re-pulverization (forexample, the first pulverization step or the second pulverization step).

FIG. 3 is a schematic drawing showing a flow of supplying a pulverizedpolymer to a pulverization step after a classification step, and furthermore to the same pulverization step. It is a conceptual diagram, wherethe first pulverization step is omitted in the conceptual diagram ofFIG. 2, and a dried substance is directly classified at theclassification step (the first classification step) and then only thenon-passed through substance having objective particle size is suppliedto the pulverization step.

FIG. 4 is a schematic drawing showing a flow, where a classificationstep (a first classification step) is set after the crushing step for anaggregated dried substance, for classifying to “objective particle size(for example, 850 to 150 μm)”/a non-passed through substance/finepowder, at the first classification step; only the non-passed throughsubstance is supplied to the pulverization step (the first pulverizationstep); the whole pulverized polymer is classified again at theclassification step (the second classification step) to “objectiveparticle size (for example, 850 to 150 μm)”; only the non-passed throughsubstance is supplied to the pulverization step (the secondpulverization step P); the whole pulverized polymer is classified againat the classification step (the third classification step) to “objectiveparticle size (for example, 850 to 150 μm)”/the non-passed throughsubstance/fine powder; and only the non-passed through substance iscirculated to the second pulverization step. The “objective particlesize (for example, 850 to 150 μm)” and “fine powder” obtained at thefirst classification step to the third classification step are suppliedto the next step, for example, a surface cross-linking step or a finepowder recycling step. In this case, in the case where the objectiveparticle size may include fine powder (for example, a substance passedthrough 850 μm), the fine powder removal at the classification step isarbitrary, and each classification step is divided to the non-passedthrough substance and a passed through substance. In addition, sievemesh size of the classification step, an apparatus of the pulverizationstep (for example, a roll mill and a pin pill) or conditions (forexample, roll gap) may be the same or may be changed.

FIG. 5 is a conceptual diagram, where one pulverization step and oneclassification step are further added in the conceptual diagram of FIG.4, and has further a fourth classification step and a thirdpulverization step in FIG. 4, where the non-passed through substance atthe fourth classification step is circulated to the third pulverizationstep.

FIG. 6 shows that the non-passed through substance at the fourthclassification step is circulated to the second pulverization step, inthe conceptual diagram (the non-passed through substance at the fourthclassification step is circulated to the third pulverization step) ofFIG. 5.

FIG. 7 is a conceptual diagram, where the third classification step wasomitted, in the conceptual diagram of FIG. 4, and a schematic drawingshowing a flow, where circulation is performed to the secondclassification step (of FIG. 4) (the second classification step in FIG.7), after the second pulverization step.

FIG. 8 is a conceptual diagram, where the “non-passed through substance(coarse particles)” at the first classification step is classified totwo (large and small) particle sizes (for example, 5 mm to 850 μm as asmall coarse particle, and 5 mm to non-passing through as a large coarseparticle); the obtained two kinds of “non-passed through substances” aresupplied to different pulverization steps (a pulverization step 1, and apulverization step 1′) in the conceptual diagram of FIG. 7. In theconceptual diagram of FIG. 7, the large coarse particle is supplied tothe added pulverization step 1′ (a pulverization machine at the left ofFIG. 8) and circulated to the first classification step.

FIG. 9 is a conceptual diagram, where the non-passed through substanceat the second classification step is circulated to the firstclassification step, in the conceptual diagram of FIG. 8 (the non-passedthrough substance at the second classification step is circulated to thesecond classification step via the second pulverization step).

FIG. 10 is a conceptual diagram, where the non-passed through substanceat the second classification step is supplied to the pulverization step1′ (a pulverization machine at the left of FIG. 10), and then circulatedto the first classification step, in the conceptual diagram of FIG. 8(the non-passed through substance at the second classification step iscirculated to the second classification step via the secondpulverization step).

FIG. 11 is a conceptual diagram, where the “non-passed through substance(coarse particles)” at the first classification step is classified totwo (large and small) particle sizes (for example, 5 mm to 850 μm as asmall coarse particle, and 5 mm to non-passing through as a large coarseparticle); the obtained two kinds of “non-passed through substances” aresupplied to different pulverization steps (a pulverization step 1, and apulverization step 1′), as in the conceptual diagram of FIG. 8, in theconceptual diagram of FIG. 5.

FIG. 12 is a schematic drawing showing compositions of pulverizationapparatuses (c1 and c2) and a classification apparatus (d) which can beused in the production method of the present invention. In this case,pulverization apparatuses (c1 and c2) are connected in series, and thewater-absorbent resin is equally divided to two after the pulverizationstep c1, and the pulverization step c2 (the pulverization apparatus c2)and the classification step d (the classification apparatus d) are setas two lines in parallel.

MODE FOR CARRYING OUT THE INVENTION

Explanation will be given below in detail on the production method forthe water-absorbing resin according to the present invention, however,as for other than the following exemplification, the scope of thepresent invention should not be limited to these explanations, and mayalso be changed and performed as appropriate within a scope not toimpair gist of the present invention. Specifically, the presentinvention should not be limited to the following each embodiment, andvarious changes within a scope shown in claims may be allowed, and alsoembodiments obtained by combining as appropriate technical meansdisclosed each in different embodiments are included in a technicalscope of the present invention.

[1] Definition of Terminology (a) “Water-Absorbing Resin”

In the present description, the “water-absorbing resin” means a waterswelling and water insoluble “polymer gelling agent”, having thefollowing properties. That is, as water swelling properties, it is theone having absorption capacity without load (CRC) of equal to or higherthan 5 g/g. CRC is preferably 10 to 100 g/g, and further preferably 20to 80 g/g. In addition, as water insoluble properties, water-solubleamount (Extractables) is essentially 0 to 50% by weight. Thewater-soluble amount is preferably 0 to 30% by weight, furtherpreferably 0 to 20% by weight, and particularly preferably 0 to 10% byweight.

It should be noted that the “water-absorbing resin” is not limited to apolymer form as a whole (100% by weight), and may include additives (tobe described later), in a range to maintain the above performances. Thatis, even a water-absorbing resin composition containing thewater-absorbing resin and the additives, it is generally called“water-absorbing resin” in the present invention. In the case where thewater-absorbing resin is a water-absorbing resin composition, content ofthe water-absorbing resin (polyacrylic acid (salt)-based water-absorbingresin) is preferably 70 to 99.9% by weight, more preferably 80 to 99.7%by weight, and still more preferably 90 to 99.5% by weight, relative tototal amount of the composition. As the components other than thewater-absorbing resin, from the viewpoint of water-absorbing speed orimpact resistance of powder (particles), water is preferable, andadditives to be described later may be contained, as needed.

(b) “Polyacrylic Acid (Salt)”

In the present description, the “polyacrylic acid (salt)” means apolymer containing an arbitrary graft component and acrylic acid (salt)as a principal component, as a repeating unit. Specifically, it means apolymer containing acrylic acid (salt), as the monomer excluding across-linking agent, essentially 50 to 100% by mole, preferably 70 to100% by mole, further preferably 90 to 100% by mole, particularlypreferably substantially 100% by mole. The salt as the polymeressentially contains a water-soluble salt, preferably contains amonovalent salt, more preferably contains an alkali metal salt or anammonium salt, still more preferably contains an alkali metal salt, andparticularly preferably contains a sodium salt. It should be noted thatshape of polyacrylic acid (salt) is not especially limited, however, aparticle or a powder is preferable.

(c) “EDANA” and “ERT”

“EDANA” is an abbreviation of European Disposables and NonwovensAssociations. In addition, “ERT” is an abbreviation of the measurementmethod (ERT/EDANA Recommended Test Method) for the water-absorbing resinof the European standard (it is nearly a world standard). In the presentdescription, properties of the water-absorbing resin is measured withreference to the ERT original (known literature: revised in 2002),unless otherwise specified.

(c-1) “CRC” (ERT441.2-02)

“CRC” is an abbreviation of Centrifuge Retention Capacity, meaningabsorption capacity without load (hereafter it may also be referredsimply to “absorption capacity”). Specifically, it is specified asabsorption capacity (unit; g/g) after free swelling 0.200 g of thewater-absorbing resin in non-woven fabric in 0.9% by weight of salinesolution for 30 minutes, and then water rinsing by a centrifugalseparation machine (under 250 G).

(c-2) “AAP” (ERT442.2-02)

“AAP” is an abbreviation of Absorbency Against Pressure, meaningabsorption capacity with load. Specifically, it is specified asabsorption capacity (unit; g/g) after swelling 0.900 g of thewater-absorbing resin in 0.9% by weight of saline solution, under a loadof 1.9 kPa for 1 hour. It should be noted that in the present inventionand Examples, AAP was measured under a load of 4.8 kPa.

(c-3) “Extractables” (ERT470.2-02)

“Extractables” means amount of water-soluble components (solublecomponents). Specifically, it is a value (unit; % by weight) measured asa dissolved polymer amount by pH titration, after adding 1.000 g of thewater-absorbing resin in 200 ml of 0.9% by weight of saline solution andstirring for 16 hours.

(c-4) “PSD” (ERT420.2-02)

“PSD” is abbreviation of Particle Size Distribution, meaning particlesize distribution measured by sieve classification. It should be notedthat weight average particle diameter and particle diameter distributionwidth are measured by a similar method to “(1) Average Particle Diameterand Distribution of Particle Diameter” described in EP No. 0349240specification (page 7, lines 25 to 43) or WO 2004/069915.

(c-5) Others

pH (ERT400.2-02): It means pH of the water-absorbing resin.

Moisture Content (ERT430.2-2): It means water content of thewater-absorbing resin:

Flow Rate (ERT450.2-02): It means flowing speed of the water-absorbingresin powder.

Density (ERT460.2-02): It means density of the water-absorbing resin.

(d) “Water-Absorbing Agent”

In the present description, the “water-absorbing agent” means a gellingagent of aqueous liquid, composed of the water-absorbing resin as themain component. It should be noted that said aqueous liquid may not onlybe water but also urine, blood, excrement, waste liquid, moisture orsteam, ice, a mixture of water and an organic solvent and/or aninorganic solvent, rain water, underground water or the like, and is notespecially limited, as long as it contains water. Among these, urine, inparticular, human urine is preferable. Content of the water-absorbingresin (a polyacrylic acid (salt)-based water-absorbing resin) accordingto the present invention is preferably 70 to 99.9% by weight, morepreferably 80 to 99.7% by weight, and still more preferably 90 to 99.5%by weight, relative to total weight of the water-absorbing agent. Ascomponents other than the water-absorbing resin, from the viewpoint ofwater-absorbing speed or impact resistance of powder (particles), wateris preferable, and additives to be described later are contained asneeded.

(e) “Others”

In the present description, “X to Y” showing a range means “equal to orlarger than X to equal to or smaller than Y”. In addition, “ton” as aunit of weight means “metric ton”. Still more, unless otherwisespecified, “ppm” means “ppm by weight” or “ppm by mass”.

Still more, measurement of properties of the water-absorbing resin isperformed, unless otherwise specified, under conditions of a temperatureof 20 to 25° C. (it may also be referred to simply as “roomtemperature”, or “normal temperature”), and a relative humidity of 40 to50%.

[2] Production Method for the Water-Absorbing Resin (1) PolymerizationStep

The present step is a step for polymerizing an aqueous solution ofacrylic acid (salt) to obtain a hydrogel-like cross-linked polymer.

(a) Monomer (Excluding a Cross-Linking Agent)

The water-absorbing resin according to the present invention uses anaqueous solution of acrylic acid (salt), as a raw material (monomer)thereof. Said aqueous solution contains acrylic acid and/or a saltthereof as a main component. In addition, it is preferable that thehydrogel-like cross-linked polymer (hereafter may be referred to also as“hydrogel”) obtained by polymerization is neutralized in at least partof the acid groups of the polymer, from the viewpoint of water-absorbingcharacteristics or amount of a residual monomer. Such apartially-neutralized salt of acrylic acid is not especially limited,however, from the viewpoint of water-absorbing performance of thewater-absorbing resin, it is preferably a monovalent salt of acrylicacid selected from an alkali metal salt, an ammonium salt, and an aminesalt of acrylic acid, more preferably an alkali metal salt of acrylicacid, furthermore preferably an acrylate salt selected from a sodiumsalt, a lithium salt, a potassium salt, and particularly preferably asodium salt.

Therefore, a basic substance to be used in neutralization of acrylicacid as a monomer or a polymer (hydrogel) after polymerization, is notespecially limited, however, it is preferably an alkali metal hydroxidesuch as sodium hydroxide, potassium hydroxide, lithium hydroxide, or amonovalent basic substance of a (hydrogen) carbonate such as sodium(hydrogen) carbonate, potassium (hydrogen) carbonate, and particularlypreferably sodium hydroxide.

The above neutralization may be performed on a polymer (hydrogel) afterpolymerization, or polymerization may be performed using a salt form ofacrylic acid as a monomer, however, from the viewpoint of enhancement ofproductivity or AAP (absorbency against pressure) or the like, it ispreferable to use a neutralized monomer, that is, to use a partiallyneutralized salt of acrylic acid, as a monomer.

Neutralization ratio of the above neutralization is not especiallylimited, however, it is preferably 10 to 100% by mole, more preferably30 to 95% by mole, still more preferably 50 to 90% by mole, andparticularly preferably 60 to 80% by mole. In addition, temperature inneutralization (neutralization temperature) is not especially limited,however, it is determined as appropriate at preferably 10 to 100° C.,and still more preferably 30 to 90° C. Other preferable conditions andthe like of neutralization treatment have been exemplified in thedescription of EP No. 574260 specification, and conditions described insaid publication may be applied also to the present invention.

The above monomer (including the following cross-linking agent) ispolymerized usually in a form of an aqueous solution, and solid contentconcentration thereof is usually 10 to 90% by weight, preferably 20 to80% by weight, still more preferably 30 to 70% by weight, andparticularly preferably 35 to 60% by weight. It should be noted thatpolymerization may be performed in slurry (water dispersion liquid) oversaturation concentration, however, from the viewpoint of properties, itis preferably performed in an aqueous solution with saturationconcentration or lower.

Further, to improve various properties of the obtained water-absorbingresin, starch, polyacrylic acid (salt), a water-soluble resin such aspolyethyleneimine or a water-absorbing resin, or various foaming agents(a carbonate salt, an azo compound, air bubbles and the like), asurfactant, or additives to be described later may be added to anaqueous solution of acrylic acid (salt) or hydrogel afterpolymerization, a dried substance or a powdery substance, as anarbitrary component. As the addition amount thereof, amount of thewater-soluble resin or the water-absorbing resin is preferably 0 to 50%by weight, more preferably 0 to 20% by weight, particularly preferably 0to 10% by weight, and most preferably 0 to 3% by weight, relative to100% by weight of the monomer. In addition, the above foaming agent,surfactant or additives is preferably 0 to 5% by weight, and morepreferably 0 to 1% weight, relative to 100% by weight of the monomer.

In addition, in the case of using a chelating agent, a hydroxycarboxylic acid or a reductive inorganic salt, used amount thereof ispreferably 10 to 5000 ppm by weight, more preferably 10 to 1000 ppm byweight, still more preferably 50 to 1000 ppm by weight, particularlypreferably 100 to 1000 ppm by weight, relative to total amount of 100%by weight of the obtained water-absorbing resin. Among these, use of thechelating agent is preferable. By using the chelating agent, enhancementof color stability (color stability in the case of long period ofstoring under high temperature and high humidity condition), or urineresistance (prevention of gelling deterioration) of the water-absorbingresin can be attained. As the above chelating agent, those exemplifiedin U.S. Pat. No. 6,599,989 specification or WO 2008/090961 pamphlet orthe like are applicable, and among them, an aminocarboxylic acid-basedmetal chelating agent or a polyvalent phosphoric acid-based compound ispreferable. It should be noted that a graft polymer (for example, astarch-acrylic acid graft polymer) or a water-absorbing resincomposition obtained by using other component is also generally called apolyacrylic acid (salt)-based water-absorbing resin, in the presentinvention.

In addition, in the present invention, in the case where acrylic acid(salt) is used as a main component, a hydrophilic or hydrophobicunsaturated monomer (hereafter may also be referred to as “othermonomers”) other than acrylic acid (salt), may be contained. These othermonomers are not especially limited, however, they include, for example,methacrylic acid, (maleic anhydride) maleic acid,2-(meth)acrylamido-2-methylpropane sulfonic acid, (meth)acryloxyalkanesulfonic acid, N-vinyl-2-pyrrolidone, N-vinylacetamide, (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide,2-hydroxyethyl (meth)acrylate, methoxy polyethylene glycol(meth)acrylate, polyethylene glycol (meth)acrylate, stearyl acrylate ora salt thereof. In the case where such other monomers are used, usedamount thereof is not especially limited, as long as it is in a degreenot to impair desired characteristics, however, it is preferably 50% byweight or lower, and more preferably 0 to 20% by weight, relative to100% by weight of the total monomer.

(b) Cross-Linking Agent (Internal Cross-Linking Agent)

In the present invention, it is particularly preferable that across-linking agent (it may also be referred to as “an internalcross-linking agent”) is used, from the viewpoint of water-absorbingcharacteristics. Used amount of the internal cross-linking agent ispreferably 0.001 to 5% by mole, more preferably 0.005 to 2% by mole,still more preferably 0.01 to 1% by mole, and particularly preferably0.03 to 0.5% by mole, relative to 100% by mole of the above monomerexcluding the cross-linking agent, from the viewpoint of properties.

The internal cross-linking agent which can be used is not especiallylimited, and it can be exemplified, for example, a polymerizablecross-linking agent with acrylic acid; a reactive cross-linking agentwith a carboxylic group; or a cross-linking agent having both thereof.Specifically, as the polymerizable cross-linking agent, a compoundhaving at least two polymerizable double bonds in a molecule can beexemplified such as N,N′-methylenebisacrylamide, (poly)ethylene glycoldi(meth)acrylate, (polyoxyethylene) trimethylolpropanetri(meth)acrylate, poly(meth)allyoxy alkane, or the like. In addition,as the reactive cross-linking agent, a covalent bonded-typecross-linking agent, such as polyglycidyl ether (ethylene glycoldiglycidyl ether or the like), polyol (propane diol, glycerin, sorbitolor the like), and an ion-bonded cross-linking agent, which is a compoundof a polyvalent metal, such as aluminum, are exemplified. Among these,from the viewpoint of water-absorbing characteristics, the abovepolymerizable cross-linking agent with acrylic acid is preferable, andin particular, an acrylate-type, allyl-type or acrylamide-typepolymerizable cross-linking agent is used preferably. These internalcross-linking agents may be used alone or may be used in combination oftwo or more kinds.

(c) Polymerization Initiator

A polymerization initiator to be used in the present invention may beselected as appropriate depending on polymerization mode. As such apolymerization initiator, for example, a photodecomposition-typepolymerization initiator, a thermal decomposition-type polymerizationinitiator, and a redox-type polymerization initiator or the like areexemplified. Used amount of the polymerization initiator is preferably0.0001 to 1% by mole, and more preferably 0.001 to 0.5% by mole,relative to 100% by mole of the monomer.

As the photodecomposition-type polymerization initiator, for example, abenzoin derivative, a benzyl derivative, an acetophenone derivative, abenzophenone derivative, and an azo compound or the like areexemplified. In addition, as the thermal decomposition-typepolymerization initiator, for example, a persulfate salt (sodiumpersulfate, potassium persulfate, ammonium persulfate), a peroxide(hydrogen peroxide, t-butyl peroxide, methyl ethyl ketone peroxide), andan azo compound (2,2′-azobis(2-amidinopropane) dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride or the like) orthe like are exemplified. In addition, among these radicalpolymerization initiators, the persulfate salt, the peroxide, and theazo compound may also be used as a photopolymerization initiator.

As the redox-type polymerization initiator, for example, a combinedsystem of the above persulfate salt or the peroxide with a reducingcompound such as L-ascorbic acid or sodium hydrogen sulfite, may beexemplified. In addition, combined use of the abovephotodecomposition-type initiator and the above thermaldecomposition-type polymerization initiator is also included as apreferable embodiment.

(d) Polymerization Method

As the polymerization method according to embodiments of the presentinvention, spray polymerization or droplet polymerization may be allowedfrom the viewpoint of performance of the water-absorbing resin, such asliquid permeability or water-absorbing speed, or easiness of control ofpolymerization, however, preferably, aqueous solution polymerization orreverse phase suspension polymerization is usually performed. Amongthese polymerization methods, aqueous solution polymerization, which hasconventionally been difficult in control of polymerization orimprovement of coloring, is preferable, continuous aqueous solutionpolymerization is more preferable, and continuous aqueous solutionpolymerization performed at high concentration and at a high initiationtemperature, is particularly preferable. Still more, suitable control ispossible in continuous polymerization and continuous production (thedrying step to the surface cross-linking step) for producing thewater-absorbing resin by a large scale, such as 0.5 t/hr or more, morepreferably 1 t/hr or more, still more preferably 5 t/hr or more, andparticularly preferably 10 t/hr or more, by polymerization of a monomeraqueous solution in one line.

As a preferable mode of the continuous aqueous solution polymerization,for example, there are included continuous kneader polymerization(described in U.S. Pat. No. 6,987,151, U.S. Pat. No. 6,710,141 or thelike), or continuous belt polymerization (described in U.S. Pat. No.4,893,999, U.S. Pat. No. 6,241,928, US-A-2005/215734 or the like). Inthese continuous aqueous solution polymerization, the water-absorbingresin can be produced in high productivity, but there is observedtendency of variation of properties (increase in the standard deviation)with scale up, however, the present invention overcomes also such aproblem.

According to the present invention, because the water-absorbing resinwith superior stability of a monomer and high whiteness can be obtained,even in polymerization under such high concentration or hightemperature, effect is exerted still more significantly under suchcondition. Such polymerization initiated at such high temperature hasbeen exemplified in U.S. Pat. No. 6,906,159 and U.S. Pat. No. 7,091,253or the like, however, according to the production method of the presentinvention, also stability of a monomer before polymerization isexcellent, and thus production in an industrial scale is easy.

These polymerization can be performed even under air atmosphere,however, from the viewpoint of improvement of coloring, it is preferableto be performed under inert gas atmosphere such as nitrogen or argon(for example, under an oxygen concentration of 1% by volume or lower).In addition, it is preferable that a monomer or an aqueous solutioncontaining the monomer is used in the polymerization after dissolvedoxygen therein is sufficiently replaced with inert gas (for example, toan oxygen concentration below 1 [mg/L]). Even by such deaeration,stability of the monomer is excellent, gelling before polymerizationseldom occurs, and the water-absorbing resin having higher propertiesand higher whiteness can be provided.

(2) Gel Crushing Step

The hydrogel-like cross-linked polymer (hydrogel) obtained in the abovepolymerization step may be supplied to a drying step (to be describedlater) as it is, however, from the viewpoint of water-absorbing speed orliquid permeability, it is crushed to become a particulate state, usinga crushing machine (a kneader, a meat chopper, or the like), as needed,during the polymerization or after the polymerization. That is, weightaverage particle diameter (specified by sieving classification) of theparticulate hydrogel after the above gel crushing is in a range ofpreferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and still morepreferably 1 to 3 mm.

Temperature of the hydrogel in gel crushing, from the viewpoint ofproperties, is warmed or heated in a range of preferably 40 to 95° C.,and more preferably 50 to 80° C. Solid content of the hydrogel is notespecially limited, however, from the viewpoint of properties, it ispreferably 20 to 80% by weight, more preferably 30 to 70% by weight, andstill more preferably 40 to 60% by weight.

(3) Drying Step

In the drying step, the above hydrogel is dried to obtain a driedpolymer. Resin solid content of the dried polymer determined from weightreduction in drying (1 g of powder or particles is heated at 180° C. for3 hours) is adjusted in a range of preferably 80% by weight or more,more preferably 85 to 99% by weight, still more preferably 90 to 98% byweight, and particularly preferably 92 to 97% by weight.

Drying temperature is not especially limited, however, it may be setpreferably within a range of 100 to 300° C., and more preferably withina range of 150 to 250° C. As the drying method, various methods can beadopted, such as heating drying, hot air drying, reduced pressuredrying, infrared ray drying, microwave drying, rotating drum-type drying(for agitated-drying gel in the heated rotating drum), agitated-dryingwith a rotor, drum dryer drying, azeotropic dewatering with ahydrophobic organic solvent, high humidity drying using high temperaturesteam in hot air drying, and the like. Drying is performed in acontinuous system or a rotation system (batch system in another name),and preferably it is performed by continuous-type drying. Preferably, itis hot air drying, in particular, hot air drying using vapor having adew point of particularly 40 to 100° C., more preferably a dew point of50 to 90° C. In the hot air drying, a through flow band-type dryingmachine is adopted, and other drying machine may be used in combination,as needed.

In the case of drying the above particulate hydrogel (having a weightaverage particle diameter of, for example, 0.1 to 10 mm), shape of thedried polymer is usually particulate or aggregate thereof (for example,a block-like substance; refer to PATENT LITERATURE 1), however, it isnot especially limited. Size of particle of a dried substance isdetermined by the particle diameter of hydrogel before drying, andshrinkage ratio of the particle diameter before and after drying can bedetermined also by calculation from the water content. An aggregatedsubstance obtained at the drying step may be supplied as it is to thepulverization step, however, it is crushed (an aggregated state isloosened) as needed at the exit of the drying machine to become aparticulate again having a weight average particle diameter of 50 mm orsmaller, 30 mm or smaller, 0.1 to 10 mm, preferably 0.5 to 5 mm, andstill more preferably 1 to 3 mm, to be supplied to the next step, inparticular, the pulverization step. It should be noted that, in the caseof drying the particulate hydrogel, in particular, in the case of dryingin a laminated state, and still more in through flow band-type drying,it is preferable to set a crushing step before the pulverization step ora transportation step to the pulverization step, because it becomes anaggregated substance, in particular, a block-like substance, composed ofdried particles of the particulate hydrogel. For crushing, a low speedpin-type crushing machine is used as appropriate. In this description,the crushing step means an operation of loosening the dried aggregatesubstance, in particular, the block-like dried aggregate substance toabout a size (weight average particle diameter) or more of the driedparticle before aggregation, in the above range (preferably 50 mm orsmaller, 0.5 to 5 mm, and still more about 1 to 3 mm), and in this case,even when apart of the dried substance is pulverized but has, as awhole, about a size (weight average particle diameter) or more of onedried particle (primary particle), it is called the crushing step, andis thus different concept from the pulverization step to be describedlater, that is, a pulverization (crushing) operation of the driedsubstance (particularly, the dried particle (primary particle) or thedried aggregated substance thereof) to objective particle size. Thus,the dried substance crushed as needed is a particulate dried substanceor an aggregate thereof (preferably 50 mm or smaller), and is still moresupplied to the pulverization step or the classification step via thetransportation step (preferably a pneumatic transportation step)(reference: FIG. 4 to FIG. 11, which include the crushing step).

(4) Pulverization Step

The present invention is characterized that circulation amount in thepulverization step is set at a certain level or more to enhance liquidpermeability or water-absorbing speed. Means for controlling thecirculation amount in the pulverization step to certain level or more isattained by supplying again at least a part of the classified polymer tothe same or different pulverization step.

That is, according to one aspect of the present invention, there isprovided a method for producing water-absorbing resin powder,sequentially having: a polymerization step for polymerizing an aqueoussolution of acrylic acid (salt) to obtain a hydrogel-like cross-linkedpolymer; a drying step for drying the obtained hydrogel-likecross-linked polymer to obtain a dried polymer; a pulverization step forpulverizing the obtained dried polymer with a pulverizing means toobtain a pulverized polymer; a classification step for classifying theobtained pulverized polymer to obtain a classified polymer; and asurface cross-linking step for surface cross-linking the obtainedclassified polymer, characterized in that, at least a part of theclassified polymer is supplied again to the same or differentpulverization step, before the surface cross-linking step, whereincirculation pulverization ratio in the pulverization step is larger than1.50.

It should be noted that “pulverization” in the present invention is astep for grain refining particles or the aggregate substance thereof;the crushing step (loosening of the aggregate) of the aggregateperformed at the exit of a band drying machine or the like is notincluded to the pulverization step; preferably a roll-type pulverizationmachine is used as the pulverization machine; and other pulverizationmachines (for example, a pin mill) and the like may be used for smallamount as needed. It should be noted that, in pulverization mainly withthe roll-type pulverization machine, in particular, in pulverization ofan amount of 80% by weight or more, particularly 90% by weight or more,there is no practical problem in specifying circulation pulverizationratio of the present invention by circulation pulverization ratio at thepulverization step using the roll-type pulverization machine. Inaddition, as described in a patent literature (U.S. Pat. No. 6,562,879),grinding and pulverizing are different concepts.

(Circulation Pulverization Ratio)

In the present invention, “circulation pulverization ratio” isrepresented by the following equation:

(Circulation pulverization ratio)=(total supply amount of thewater-absorbing resin to the pulverization step)/(total discharge amountof the water-absorbing resin at the drying step)  [EXPRESSION 2]

wherein (total supply amount of the water-absorbing resin to thepulverization step)=(total discharge amount of the water-absorbing resinat the drying step)+(amount of the classified polymer supplied again tothe same or different pulverization step).

It is specified by pulverized amount using the same or differentpulverization machine, and in continuous pulverization, it is specifiedby pulverized amount [kg/hr] in equilibrium. In the present description,there may be the case where effect of the present invention is small ina small scale, and the feature of circulation pulverization ratio in thepresent invention is suitably applicable to a range of the above largescale (1 [t/hr]) or more.

In the present description, the circulation pulverization ratio of 1.50or lower provides inferior liquid permeability (for example, SFC) of thewater-absorbent resin, and largely increases fine powder after damage,too, and thus it is not preferable. On the other hand, by controllingthe circulation pulverization ratio at a value larger than 1.50, liquidpermeability (for example, SFC) of the water-absorbent resin can beenhanced, while suppressing decrease in damage resistance thereof to theminimum.

It should be noted that increase in fine powder after damage isspecified by the measurement method of the Examples, and even when theamount of fine powder (for example, passed through substance of the JISstandard sieve of 150 μm) is small just after the production of thewater-absorbing resin, fine powder generates by process damage inproducing the disposable diapers, which gives adverse influence such asdecrease in liquid permeability, in practical use of the disposablediapers, therefore it is not preferable.

In the present invention, in view of the liquid permeability (forexample, SFC), the lower limit of the circulation pulverization ratio ishigher than 1.50, still more preferably in the order of 1.60 or higher,1.70 or higher, 1.80 or higher, 1.90 or higher, 2.00 or higher, and 2.10or higher. On the other hand, in view of the water-absorbing speed (forexample, FSR), the upper limit of the circulation pulverization ratio ispreferably in the order of 3.00 or lower, 2.50 or lower, 2.40 or lower,2.30 or lower, 2.10 or lower, 1.90 or lower, 1.70 or lower, and 1.60 orlower.

That is, in view of balance between the water-absorbing speed and theliquid permeability, the circulation pulverization ratio is determinedas appropriate within the above range, however, it is preferably over1.50 and 3.00 or lower. Among these, to attain liquid permeability, itis controlled preferably at 1.70 to 2.80, and still more 1.90 to 2.70,and in particular, 2.10 to 2.50.

Conventionally, from the common general knowledge of pulverization, thenon-passed through substance (which is left on the sieve) afterclassification has been decreased as much as possible, relative toobjective particle size (for example, 850 to 150 μm, or a substancepassed through 710 μm), and usually it has been set below 10%(circulation pulverization ratio specified by the present invention isbelow 1.10), still more preferably below 5% (the same is below 1.05),and particularly preferably below 1% (the same is below 1.01), however,in the present invention, by increasing the non-passed through substanceafter classification, as compared with objective particle size, beforethe surface cross-linking step of the water-absorbing resin, liquidpermeability (SFC) of the water-absorbing resin can be enhanced, whilesuppressing the decrease in damage resistance after surfacecross-linking (in particular, surface cross-linking with an organicsurface cross-linking agent) at a high value.

(Control Method)

To control the circulation pulverization ratio within the above range(larger than 1.50), at least a part of the classified polymer issupplied again to the same or different pulverization step, after thepulverized polymer (the pulverized water-absorbing resin) obtained viathe pulverization step is made to a classified polymer (the classifiedwater-absorbing resin) via the classification step. The classificationstep may be wind force classification or air classification exemplifiedin WO 2008/123477 or the like, however, from the viewpoint of effect,sieve classification is preferably applied, and in that case,classification is performed using sieves with one or more kinds of sievemesh sizes. In that case, preferably, two or more kinds, still morethree or more kinds of sieves with different sieve mesh size are used inthe classification step, and the non-passed through substance (forexample, particles having a particle diameter of 850 μm or larger)including the topmost portion thereof is pulverized again, and theclassified polymer of the passed through substance (for example,particles having a particle diameter below 850 μm) is supplied to thesurface cross-linking step. Still more preferably, the non-passedthrough substance (for example, particles having a particle diameter of850 μm or larger) including the topmost portion thereof is pulverizedagain, and the passed through substance (for example, particles having aparticle diameter below 850 μm) from which fine powder (for example,particles having a particle diameter below 150 μm) is removed issupplied to the surface cross-linking step. A suitable flow is shown inFIG. 1 to FIG. 3. It should be noted that, in FIG. 1 to FIG. 12, toenhance and stabilize properties, the pulverization step or theclassification step is preferably performed at a certain temperature orhigher (still more, it is a depressurization step) to be describedlater, in addition, distance between the steps is each connectedpreferably by pneumatic transportation (at a dew point of 0° C. orlower).

Number of sieves or a sieve mesh size (μm) to be used in the presentinvention is determined as appropriate, and the sieve mesh size may beonly one kind (classification of the non-passed through substance andthe passed through substance), however, from the viewpoint of enhancingproperties, different large and small sieve mesh sizes of two or morekinds, preferably 3 to 6 kinds, and still more preferably 4 to 6 kindsare used, wherein the sieve mesh sizes are selected as follows: a largersieve with 710 to 200 μm, a middle sieve with 850 to 150 μm, a smallersieve with 300 to 45 μm, still more 250 to 106 μm or the like. Inaddition, in the present invention, for objective particle size (forexample, 850 to 150 μm), a sieve for removing the non-passed throughsubstance (or a sieve for removing fine powder) may be only one (forexample, 850 μm), and may still be two or more kinds (in particular, twokinds, for example, 850 μm and 2 mm), and also as a sieve for finepowder removal, one kind or two or more kinds (in particular, two kinds)are used similarly.

(Circulation to the Same or Different Pulverization Step (aPulverization Machine))

In the present description, as shown in FIG. 1, it is preferable thatpredetermined amount of the classified polymer via the classificationstep, in particular, predetermined amount of the non-passed throughsubstance is supplied again to the same pulverization step before theclassification step. In the present description, in classification ofthe non-passed through substance having objective particle size,classification of 100% generally requires a long period of time,therefore it may be allowed that object particle size (for example, 850to 150 μm) or fine powder (150 μm) is included in some degree in thenon-passed through substance (for example, 850 μm or larger) to beremoved. In addition, also as for classification to the object particlesize, fine powder may be included in some degree. By circulation usingthe same pulverization machine, properties can be enhanced, such asliquid permeability or damage resistance, without requiring use of a newpulverization means. In the case where the classified polymer issupplied to the same pulverization machine, circulation pulverizationratio can be specified, by dividing total supply amount (derived fromthe drying step and derived from the circulation step) to such onepulverization machine, by amount of the dried substance. In the presentdescription, to solve the problem of the present invention, preferably,the pulverization means is a roll-type pulverization machine to bedescribed later. It is preferable that pulverization with the same ordifferent roll-type pulverization machine is performed, also beforecirculation and after circulation. It should be noted that, in the caseof using a different roll-type pulverization machine in thepulverization step after circulation, size or conditions of eachpulverization machine may be different or the same.

In addition, as shown in FIG. 2 or FIG. 3, it is also preferable thatthe classified polymer is supplied to a different classification step(the second classification step) via a different pulverization step (thesecond pulverization step). In the present description, in the case ofcirculation to a different pulverization machine (at or subsequent tothe second pulverization step), that is, in the case of supplying theclassified polymer to a different pulverization machine, circulationpulverization ratio can be specified, by dividing total supply amount tosuch a plurality of pulverization machines (derived from the drying stepand derived from the circulation step; for example, the pulverizationmachine 1 and the pulverization machine 2), by amount of the driedsubstance. In the present description, to solve the problem of thepresent invention, preferably, any of the pulverization machines is aroll-type pulverization machine to be described later. Still more, inthe case where the classified polymer is supplied to a differentpulverization machine (the second pulverization machine/the secondpulverization step) or to a different pulverization machine andclassification machine (the second pulverization machine and the secondclassification machine), in the circulation step of the presentinvention, by adopting setting condition of such pulverization step at adifferent condition from the pulverization step before circulation andthe circulation step (the first pulverization machine and the firstclassification machine), control of particle diameter becomes easy, andstill more properties of the obtained water-absorbing resin can also beenhanced. That is, multi-stage pulverization (preferably, a roll-typepulverization machine) and/or (preferably, and) multi-stageclassification (preferably, sieve classification), shown in FIG. 2 orFIG. 3, are preferable from the viewpoint of enhancing properties of theobtained water-absorbing resin. In the present description, themulti-stage shall be 2 or more stages (2 or more units of thepulverization machines and classification machines in series),preferably 2 to 10 stages (2 to 10 units in series), stillmorepreferably 2 to 6 stages (2 to 6 units in series), and particularlypreferably 3 to 5 stages (3 to 5 units in series).

That is, as the most preferable embodiment, multi-stage pulverization(preferably, a roll-type pulverization machine) and multi-stageclassification (preferably, sieve classification) are exemplified, wherethe pulverization step and the classification step shown in FIGS. 5, 6and 11 or the like are repeated, and preferable number of stages iswithin the above range. In the present description, in the multi-stagepulverization (for example, including the first pulverization step andthe subsequent steps), the roll-type pulverization machine is preferablyused respectively, and in that case, the roll of the pulverizationmachine at each pulverization steps may be 1 stage (1 pair) or may bemulti-stage (2 or more pairs).

In addition to the above-mentioned FIG. 2 and FIG. 3, in a similarmanner, in FIG. 4 to FIG. 11, a plurality of pulverization steps and aplurality of classification steps are connected in series, and only theno-passed through substance via the classification step (coarserparticles than objective particle size) is supplied to the differentpulverization step. Fine powder becomes reduced and an apparatus hassmall load and can be made compact, and still more, properties (forexample, liquid permeability or water-absorbing speed) of thewater-absorbing resin enhances, as compared with a method where thewhole amount is still more pulverized, and thus it is preferable. In thecase where such a plurality of pulverization steps and a plurality ofclassification steps are connected in series, and only the no-passedthrough substance (coarser particles than objective particle size) viathe classification step is supplied to the different pulverization step,properties of the water-absorbing resin are enhanced more, as well asfine powder of the water-absorbing resin other than objective becomesreduced, and still more load of the pulverization step and theclassification step can be lowered, and thus it is preferable. In thepresent description, the pulverization steps and the classificationsteps to be connected in series, hereafter, may generally be calledsequentially a first classification step, a second classification step,a third classification step, - - - , a first pulverization step, asecond pulverization step, a third pulverization step, - - - , however,in the present invention, sieve mesh sizes of a plurality of theclassification steps, apparatuses (for example, a roll mill and a pinmill) or conditions (for example, roll gap) of the pulverization stepsmay be the same or may be changed respectively.

In addition, “objective particle size (for example, 850 to 150 μm)” and“fine powder” obtained preferably in the classification step (or theclassification step at and the subsequent to the second classificationstep), in the present invention, is supplied to the next step, forexample, to the surface cross-linking step or the fine powder recyclingstep. In the present description, in the case where the objectiveparticle size may contain fine powder (for example, the substance passedthrough 850 μm), the fine powder removal at the classification step isarbitrary; each classification step divides to the non-passed throughsubstance and a passed through substance; the non-passed throughsubstance is pulverized again; and the passed through substance issubjected to surface cross-linking or is adopted as a product as it is.In addition, the water-absorbing resin with the objective particle size,obtained at each classification step, is supplied, preferably, to thesurface cross-linking step as the next step, however, it may be adoptedas a product as it is without surface cross-linking, or may be subjectedto a modification step (for example, coating with a polymer, asurfactant, inorganic fine particles or the like) other than surfacecross-linking.

Specifically, in FIG. 2, there are provided the first and the secondclassification steps and the first and the second pulverization steps,where after supplying only the non-passed through substance at the firstclassification step to the second pulverization step, it is classifiedagain at the second classification step to “objective particle size (forexample, 850 to 150 μm)”/a non-passed through substance/fine powder;only the non-passed through substance is supplied to the pulverizationstep (the second pulverization step P); and (although not shown) thenon-passed through substance is supplied to re-pulverization (forexample, the first pulverization step or the second pulverization step)as needed.

FIG. 3 is a schematic drawing showing a flow of supplying a pulverizedpolymer again to a different pulverization step after classification andstill more to the same pulverization step. It is a conceptual diagram,where the first pulverization step is omitted in the conceptual diagramof FIG. 2, and a dried substance is directly classified at theclassification step (the first classification step) and then only thenon-passed through substance having objective particle size is suppliedto the pulverization step.

FIG. 4 is a schematic drawing showing a flow, where a classificationstep (the first classification step) is set after the crushing step foran aggregated dried substance, for classifying to “objective particlesize”/a non-passed through substance/fine powder at the firstclassification step; only the non-passed through substance is suppliedto the pulverization step (the first pulverization step); the wholepulverized polymer is classified again at the classification step (thesecond classification step) to “objective particle size”/a non-passedthrough substance/fine powder; only the non-passed through substance issupplied to the pulverization step (the second pulverization step); thewhole pulverized polymer is classified again at the classification step(the third classification step) to “objective particle size (forexample, 850 to 150 μm)”/the non-passed through substance/fine powder;and only the non-passed through substance is circulated to the secondpulverization step.

FIG. 5 is a conceptual diagram, where one pulverization step and oneclassification step are further added in the conceptual diagram of FIG.4, and has further a fourth classification step and a thirdpulverization step in FIG. 4, where the non-passed through substance atthe fourth classification step is circulated to the third pulverizationstep.

FIG. 6 is a conceptual diagram, where the non-passed through substanceat the fourth classification step is circulated to the secondpulverization step, in the conceptual diagram of FIG. 5 (the non-passedthrough substance at the fourth classification step is circulated to thethird pulverization step).

FIG. 7 is a conceptual diagram, where the third classification step wasomitted, in the conceptual diagram of FIG. 4, and is a schematic drawingshowing a flow, where circulation is performed to the secondclassification step (of FIG. 4) (the second classification step in FIG.7), after the second pulverization step.

FIG. 8 is a conceptual diagram, where the “non-passed through substance(coarse particles)” at the first classification step is classified totwo (large and small) particle sizes (for example, 5 mm to 850 μm as asmall coarse particle, and 5 mm to non-passing through as a large coarseparticle); the obtained two kinds of “non-passed through substances” aresupplied to different pulverization steps (a pulverization step 1, and apulverization step 1′) in the conceptual diagram of FIG. 7. In theconceptual diagram of FIG. 7, the large coarse particle is supplied tothe added pulverization step 1′ (a pulverization machine at the left ofFIG. 8) and circulated to the first classification step.

FIG. 9 is a conceptual diagram, where the non-passed through substanceat the second classification step is circulated to the firstclassification step, in the conceptual diagram of FIG. 8 (the non-passedthrough substance at the second classification step is circulated to thesecond classification step via the second pulverization step).

FIG. 10 is a conceptual diagram, where the non-passed through substanceat the second classification step is supplied to the pulverization step1′ (a pulverization machine at the left of FIG. 10), and then circulatedto the first classification step, in the conceptual diagram of FIG. 8(the non-passed through substance at the second classification step iscirculated to the second classification step via the secondpulverization step).

FIG. 11 is a conceptual diagram, where the “non-passed through substance(coarse particles)” at the first classification step is classified totwo (large and small) particle sizes (for example, 5 mm to 850 μm as asmall coarse particle, and 5 mm to non-passing through as a large coarseparticle); the obtained two kinds of “non-passed through substances” aresupplied to different pulverization steps (a pulverization step 1, and apulverization step 1′), as in the conceptual diagram of FIG. 8, in theconceptual diagram of FIG. 5.

In the present invention, using the above-mentioned FIG. 1 to FIG. 11 aspreferable representative examples, it is preferable that a plurality ofpulverization steps and a plurality of classification steps areconnected in series (if needed, a part can be branching in parallel),and only the non-passed through substance via the classification step(coarser particles than objective particle size) is supplied to adifferent pulverization step. That is, in the present invention, thewater-absorbing resin to be circulated has been dried and pulverized.Conventionally, there has been known also technology for removing and,as needed, pulverizing and re-drying a non-dried substance after drying(PATENT LITERATURES 3 to 5), however, PATENT LITERATURES 1 to 5 do notdisclose a circulation pulverization ratio of 1.50 or larger, and in thepresent invention, the classified polymer of the dried substance(preferably having a water content of 10% by weight or lower, 8% byweight or lower, still more 6% by weight or lower, in particular, 4% byweight or lower) is preferably supplied directly to the pulverizationstep as it is, not to the drying step. Different from the PATENTLITERATURES 3 to 5, where the non-dried substance is removed, in thepresent invention, the classified polymer to be circulated again to sucha pulverization step (preferably, a roll-type pulverization machine andpreferably under reduced pressure) is a dried substance (water contentof 10% by weight or lower) containing a portion of preferably 10 mm orsmaller, 5 mm or smaller, 3 mm or smaller and 2 mm or smaller, in anamount of preferably 80% by weight or more, and particularly preferably90% by weight or more.

(Production Amount)

Effect of the present invention is exerted significantly in productionor industrial continuous production of the water-absorbing resin withhigh liquid permeability, in particular, in continuing 24 hours or moreof a large scale continuous production of the water-absorbing resin withan FSR of a specified value or higher, rather than in a small scale ofan experimental room level. Accordingly, preferable production amount iswithin the above range.

(Pulverization Machine)

A pulverization machine to be used in the pulverization step includes aconventionally known pulverization machine such as a roll mill, a hammermill, a roll granulator, a jaw crusher, a Gyratory crusher, a conecrusher, a roll crusher, and a cutter mill. From the viewpoint ofparticle size control, a roll-type pulverization machine such as theroll mill or the roll granulator is used particularly preferably inmulti-stage (preferably 2 to 10 stages, and more preferably 2 to 4stages). It should not be noted that, in the case of using the roll-typepulverization machine in multi-stage, a plurality of the roll-typepulverization machines may be connected up and down, or, as shown in theabove FIG. 2 to FIG. 11, after a one-stage roll-type pulverizationmachine, another one-stage roll-type pulverization machine may beinstalled with sandwiching the classification step between them, andalso this case shall be encompassed in the concept of the multi-stagepulverization (multi-stage roll-type pulverization machines) so calledin the present invention.

That is, among these pulverization machines, use of the roll-typepulverization machine is preferable in the pulverization step. In stillmore other preferable embodiment, the roll-type pulverization machineand another pulverization machine are used in combination in thepulverization step. In addition, it is preferable that thesepulverization steps are performed under reduced pressure of thefollowing range. By operation under reduced pressure, liquidpermeability (SFC) is enhanced more. Preferable degree of reducedpressure is as described below.

In the roll-type pulverization machine, diameter of a roller (forexample, 10 to 1000 mm), length (100 to 5000 mm), pitch, clearance, rollgap, roller material, pressure range between rollers (nearly 0 to over80 N/mm), roller speed, speed ratio (constant speed or non-constantspeed), scraper, pitch, clearance, and the like may be determined asappropriate.

(Reduced Pressure State)

In the present invention, from the viewpoint of properties enhancement(example: absorbency against pressure, liquid permeability) orpulverization efficiency, the pulverization step is preferably performedunder reduced pressure, and still more preferably, the classificationstep is also performed under reduced pressure. In the presentdescription, “a reduced pressure state” means that air pressure is in astate lower than atmospheric pressure, and is represented by a plusvalue of “a degree of reduced pressure”. That is, provided thatatmospheric pressure is standard air pressure (101.3 kPa), “a degree ofreduced pressure is 10 kPa” means that air pressure is 91.3 kPa. In thepresent invention, the lower limit of the degree of reduced pressure ispreferably over 0 kPa, more preferably 0.01 kPa or higher, and stillmore preferably 0.05 kPa or higher. In addition, from the viewpoint ofpreventing hanging up of a powder in a classification apparatus, andcost reduction of an discharge apparatus or the like, the upper limit ofthe degree of reduced pressure is usually 30 kPa or lower, preferably 10kPa or lower, more preferably 5 kPa or lower, and still more preferably2 kPa or lower. A preferable numerical value range of degree of reducedpressure may be selected arbitrarily between the above upper limit valueand the lower limit value.

(Heating)

In the present invention, from the viewpoint of properties enhancement(example: absorbency against pressure, liquid permeability), thepulverization step is preferably performed at certain temperature orhigher, and still more preferably, the classification step is alsoperformed at certain temperature or higher. In the present invention, itis set at preferably 35° C. or higher, and still more 40 to 100° C., 50to 90° C., and 60 to 80° C. To maintain such a certain temperature orhigher, the pulverization step and/or the classification step are heated(external heating) or warmed (preferably, made heat insulation).

It should be noted that temperature of the pulverization step or theclassification step is specified by temperature of the inside surface ofthe apparatus or of the water-absorbing resin (the classified polymer,the pulverized polymer), and preferably temperature of thewater-absorbing resin (the classified polymer, the pulverized polymer),still more temperature of both of the inner surface of the apparatus areset at the above temperature. As a means for controlling the temperatureof the water-absorbent resin at the above range, the water-absorbentresin may be in a heated state including by heat radiation or coolingfrom completion of the drying step (if needed, it can be warmed orheated after the drying step). In addition, a means for controlling thetemperature of the pulverization machine or the classification machineat the above range may be heat transfer from the water-absorbent resinat the above range, or may be warming or heating of the apparatus asappropriate.

(Particle Size)

In the present invention, by obtaining the water-absorbing resin havingan objective particle size via the pulverization step and theclassification step (still more, by mixing the water-absorbing resinfrom a plurality of the classification steps as needed), particle sizeis controlled, and preferably surface cross-linking is furtherperformed. Weight average particle diameter (D50) before surfacecross-linking is adjusted at 200 to 600 μm, preferably 200 to 550 μm,more preferably 250 to 500 μm, and particularly preferably 350 to 450μm. In addition, the less is the particles having a particle diameterbelow 150 μm is the better, and it is adjusted usually at 0 to 5% byweight, preferably 0 to 3% by weight, and particularly preferably 0 to1% by weight. Still more, the less is the particles having a particlediameter 850 μm or larger (still more, 710 μm or larger) is the better,and it is adjusted usually at 0 to 5% by weight, preferably 0 to 3% byweight, and particularly preferably 0 to 1% by weight. In addition, inthe present invention, surface cross-linking is performed at a ratio ofthe particles having a particle diameter of 850 to 150 μm, still moreratio of the particles having a particle diameter of 710 to 150 μm, ispreferably 95% by weight or more, still more 98% by weight or more (theupper limit is 100% by weight). Logarithm standard deviation (σζ) of theparticle size distribution is set at 0.25 to 0.45, preferably 0.30 to0.40, and more preferably 0.32 to 0.38. Measurement methods for theseproperties are described in WO 2004/069915 or EDANA-ERT420.2-02, usingstandard sieves. The above particle size before surface cross-linking isalso applied preferably to after surface cross-linking, and still moreto a final product (another name: a water-absorbing agent or aparticulate water-absorbing agent). For particle size control also aftersurface cross-linking, there may be installed a classification step, acrushing step (an operation for loosening a substance aggregated at thesurface cross-linking), a granulation step (reduction of fine powder, orincrease in average particle diameter by binding particles) or the like,and preferably the classification step is installed also after surfacecross-linking.

Density (specified by ERT460.2-02) of the water-absorbing resin ispreferably 0.50 to 0.80 [g/cm³], and more preferably 0.60 to 0.70[g/cm³]. The case where density does not satisfy the above range mayprovide difficulty in control of stirring power index, decreaseproperties or increase powder in some cases.

(5) Transportation Step and Circulation Step

In the present invention, it is preferable that step between thepulverization step and the classification step, and step before andafter them are connected by a transportation apparatus. A transportationmachine to be used in the above transportation step, as thetransportation apparatus to be used, includes, for example, a beltconveyor, a screw conveyor, a chain conveyor, a vibration conveyor, apneumatic conveyor or the like, and the one provided with a heatingmeans and/or a warming means of the inner wall surface thereof fromoutside. These transportation steps are performed under reduced pressureor a pressurized state.

Among these transportation machines, pneumatic transportation ispreferable. Pneumatic transportation of the water-absorbing resin hasbeen exemplified in WO 2007/104657, WO 2007/104674, WO 2007/104676,however, among such pneumatic transportation, carrying is preferablyperformed at a dew point of 0° C. or lower. Pneumatic transportation ofthe present invention may be pressurized transportation, or may bereduced pressure transportation. Pressure to be used may be determinedas appropriate, however, it is, for example, in a range of −0.8 bar to10 bar.

In a preferable transportation method for the water-absorbing resin,pneumatic transportation is used at least at a part of step between thepulverization step and the classification step, and before and afterthem, and preferably at step between the pulverization step and theclassification step and before and after them. From the viewpoint ofmaintaining superior properties of the water-absorbing resin powderstably, it is preferable that dried air is used as primary air, andsecondary air to be used as needed. Dew point of this air is 0° C. orlower, still more −5° C. or lower, preferably −10° C. or lower, morepreferably −12° C. or lower, and particularly preferably −15° C. orlower. In considering cost performance, a range of dew point is −100° C.or higher, preferably −70° C. or higher, and still more it is enough atabout −50° C. Still more it is preferable that temperature of gas is 10to 40° C., and still more about 15 to 35° C.

Other than using dried gas (air), heated gas (air) may also be used. Aheating method is not especially limited, however, gas (air) may beheated directly using a heat source, or gas (air) to be passed may beheated indirectly by heating the transportation part or a pipeline.Lower limit temperature of this heated gas (air) is preferably 20° C. orhigher, and more preferably 30° C. or higher, while the upper limit isbelow 70° C., and more preferably below 50° C.

As a method for controlling the dew point, gas, preferably air may bedried as appropriate. Specifically, a method for using a membrane dryer,a method for using a cooling adsorption-type dryer, a method for using adiaphragm dryer, or a method for using these in combination areincluded. In the case of using the adsorption-type dryer, it may be aheating regeneration-type, or may be a non-heating regeneration-type, ormay be a non-regeneration-type.

(6) Classification Step

The water-absorbing resin powder pulverized in the above is classifiedbefore surface cross-linking, and still more also after surfacecross-linking (in particular, sieve classification), in subjecting topulverization and classification with the above circulationpulverization ratio. A sieve classification method for thewater-absorbing resin has been exemplified, for example, in U.S. Pat.No. 6,164,455 (PATENT LITERATURE 50), WO 2006/074816 (PATENT LITERATURE51), WO 2008/03672 (PATENT LITERATURE 52), WO 2008/037673 (PATENTLITERATURE 53), WO 2008/03675 (PATENT LITERATURE 54), and WO 2008/123477(PATENT LITERATURE 55). Description will be given below on a suitableclassification method applicable to the present invention, inparticular, a sieve classification method (removal of electricity or thelike).

(Classification Apparatus)

A classification apparatus to be used in the present invention is notespecially limited, as long as it has a sieve mesh face, and includes,for example, the one to be classified to a vibrating screen and ashifter. In addition, shape of the sieve mesh face is determined asappropriate from a round-type (a round-sieve), a square-type (asquare-sieve) or the like. The vibrating screen includes inclined shape,Low-head shape, Hum-mer, Rhewum, Ty-Rock, Gyrex and Eliptex or the like,and the shifter includes Reciprocating shape, Exolon-grader,Traversator-sieve, Sauer-meyer, Gyratory, Gyro-shifter and Ro-tex screenor the like. They are sub-classified by moving shape of the mesh face:circle, ellipse, linear line, arc, pseudo-ellipse, spiral; the vibrationsystem: free vibration, forced vibration; the drive method: eccentricshaft, non-even load weight, electromagnet, impact; inclination of themesh face: a horizontal system, an inclined system; the installationmethod: a floor-type, hang-down-type, or the like.

Among them, from the viewpoint of effect of the present invention, aclassification apparatus for moving the sieve mesh face in spiral ispreferable, by combination of radial inclination (inclination of a sievemesh for dispersing a material from the center to the circumference) ortangential inclination (inclination of a sieve mesh for controllingdischarge speed on the mesh), such as a oscillation system (tumblershifter, tumbler-screening machines).

(Depressurization)

To solve the problems of the present invention, it is preferable that inaddition to the pulverization step, the classification step is alsodepressurized in a similar range as explained on the pulverization step.

(Heating)

To solve the problems of the present invention, it is preferable that inaddition to the pulverization step, the classification step is alsoadjusted at a constant temperature similarly as explained on thepulverization step.

(A Classification Mesh)

In the present invention, the water-absorbing resin powder is classifiedusing a classification mesh. As the classification mesh, variousstandard sieves such as, for example, JIS, ASTM, TYLER-type and thelike, are exemplified. These sieves may be a plate sieve, or a meshsieve, and shape of the mesh sieve is selected as appropriate, withreference to JIS Z8801-1(2000) or the like. A sieve mesh size of thestandard sieve is selected from a range of 100 mm to 10 μm, and stillmore 10 mm to 20 μm, and one kind or two or more kinds of the sieves, inparticular, a metal sieve is used.

The sieve may be a classification-type only for the upper part, or aclassification-type only for the lower part, however, simultaneousclassification of the upper limit and the lower limit, that is, use of aplurality of sieves at the same time, is preferable, and use of sieveswith at least three kinds of different sieve mesh sizes is still morepreferable, from the viewpoint of properties enhancement. As such amethod, it is preferable to use an intermediate sieve or a higher levelsieve, other than the upper and lower predetermined sieves. As asuitable sieve, for example, the one having the upper limit of 850 μm,or 710 μm, or 600 μm, and the one having the lower limit of about 150μm, or 225 μm are used, and still more, a sieve may be added at themiddle or the upper part thereof.

(Classification Vibration)

A sieving apparatus suitable for the classification method in thepresent invention is not especially limited, however, it is preferableto use a plane classification method, and in particularly preferably, atumble-type sieving apparatus. This sieving apparatus is typicallyvibrated to support classification. This vibration is performed in sucha degree that a product to be classified is introduced on a sieve inspiral. These forced vibrations have an eccentricity amount of typically10 to 100 mm, and preferably 25 to 40 mm, and a rotation number of 60 to600 rpm, and preferably 100 to 400 rpm.

(Air Flow)

It is preferable that gas flow, in particularly preferably air is passedthrough on the water-absorbing resin during classification. This gasamount is typically 0.1 to 10 [m³/hr], preferably 0.5 to 5 [m³/hr], andparticularly preferably 1 to 3 [m³/hr], per 1 m² of sieve area, and inthis case, gas volume is measured under standard condition (25° C. and 1bar). Particularly preferably, gas flow is heated before introducing tothe sieving apparatus typically at least at 40° C., preferably at leastat 50° C., still more preferably at least at 60° C., speciallypreferably at least at 65° C., and particularly preferably at least at70° C. Temperature of gas flow is usually below 120° C., preferablybelow 110° C., more preferably below 100° C., still more preferablybelow 90° C., and particularly preferably below 80° C.

Dew point of airflow (gas flow) is preferably 20° C. or lower, morepreferably 15° C. or lower, still more preferably 10° C. or lower, andparticularly preferably 0° C. or lower. The lower limit value of the dewpoint is not especially limited, however, in consideration of costperformance, it is preferably about −5° C.

(Removal of Electricity)

In the present invention, preferably removal of electricity is performedin sieve classification, and still more also electricity is removed inthe pulverization step. By performing such removal of electricity,properties, in particular, liquid permeability (for example, SFC) of thesurface cross-linked water-absorbing resin enhances. Such effect isexerted significantly in production or industrial continuous productionof the water-absorbing resin with high liquid permeability, inparticular, in continuing 24 hours or more of continuous production ofthe water-absorbing resin with high SFC (for example, SFC is 10 ormore), in a scale of 1 t/hr or more, rather than in a small scale of anexperimental room level.

In the present invention, preferably removal of electricity is performedin the classification step. Removal of electricity is performed for atleast one of the classification apparatus, the water-absorbing resin andthe sieve, however, because these three are contacted each other at theclassification step, it is enough that electricity is removed from anyone of them, and preferably electricity is removed from the apparatus orthe sieve itself.

As the removal method for electricity, for example, the followingmethods (A) to (C) is applicable, however, it is not especially limitedto these. Leakage current taken out in such removal of electricity ismade flown to the earth through grounding (earth) preferably shown bythe following grounding resistance value.

(A) An electricity removal brush: removal of electricity from the sieveface where static electricity generated.(B) An ion generation brush: removal of electricity by generation ofions by applying high voltage.(C) Grounding (earth): removal of electricity of static electricitygenerated at a rotating substance, a rotating axis, a rotating body, oran apparatus.

In the case of using the above (A) electricity removal brush, aself-discharge method may be used, where a little clearance is madebetween the electricity removal brush and a charged substance, or aground leaking method may be used, where the grounded electricityremoval brush is contacted with the charged substance to take outaccumulated static electricity as leakage current. Such a electricityremoval brush is produced using stainless fiber, carbon fiber, amorphousfiber, chemical fiber, plant fiber, animal hair or the like, and wirediameter thereof is about 1 to 100 μm, still more 5 to 20 μm, and a wirelength is 1 to 100 μm, and particularly preferably it is fabricated toultra-fine stainless fiber.

For example, the above (B) includes a static eliminator (ionizer), wherecharged amount and electrification charge of the classificationapparatus or the water-absorbing resin are measured, to furnish theopposite charge to plus charge or minus charge, and to make it neutralelectrically. It is enough to attain both optimal electricity removaland ion balance control, in response to a charged state of an object. Asfor charged amount of the object, ion current may be measured using anion current detection circuit built-in in a controller. The method (B),where static electricity is made powerless by neutralization using acharge having reversed polarity, is a preferable method for thewater-absorbing resin. Such an electricity removal method generates ionsin air or other gas to neutralize the electrification charge by theions. Therefore, the electricity removal apparatus is also called anionizer.

The case of using the above (C) grounding is a method for electricityremoval, by connecting a building where an apparatus is installed, or astand to ground having a grounding resistance value shown below;electrically connecting the apparatus to the building or the stand;contacting a charged substance to the apparatus so as to take outaccumulated static electricity as leakage current. This method is simpleand easy, and has high effect because the whole apparatus works as anelectricity removal apparatus, and is thus one of the preferable methodsfor the water-absorbing resin.

A grounding resistance shows a resistance value against current flowingfrom an earth electrode, buried in soil for grounding, to the ground. Asthe measurement method, a commercial earth-resistance meter is used. Apreferable range of the grounding resistance value is 100Ω or lower,more preferably 10Ω or lower, and still more preferably 5Ω or lower.

(Guide)

In the present invention, it is also preferable that the sieve of theclassification apparatus has a guide for the water-absorbing resin.Installation of such a guide enables more efficient classification. Sucha guide apparatus works to guide or the like the water-absorbing resinpowder to the center part of the sieve, and length thereof is determinedin about 5 to 40% of the diameter.

(Material and Surface Roughness)

The material of the sieving apparatus may be selected as appropriatefrom a resin or a metal or the like, however, as compared with a sievecoated with a resin, exemplified in JP-A-11-156299, preferably the caseof a metallic sieve including a contact surface with the water-absorbingresin, in particular, a stainless sieve, exerts effect of the presentinvention more.

In addition, from the viewpoint of properties enhancement, surfaceroughness of the sieve apparatus is preferably 800 nm or smaller. Amaterial of the sieving apparatus is preferably stainless steel. Bymirror finishing of the stainless steel, properties is enhanced more.The stainless steel includes SUS304, SUS316, SUS316L or the like.

In the present invention, it is preferable that the inner surface of thesieving apparatus is controlled to have a surface roughness (Rz),specified by JIS B 0601-2001, of 800 nm or less. It is preferable to besmoothened to have a surface roughness (Rz) of preferably 150 nm orless, still more preferably 50 nm or less, and 25 nm or less. It shouldbe noted that Rz means the maximum value of the maximum height (μm) ofsurface irregularity. Such surface roughness may be measured inaccordance with JIS B 0651-2001, using a stylus type surface roughnessmeasuring meter.

(7) Fine Powder Recycling Step

In the present invention, fine powder is preferably recycled. That is, apreferable embodiment further includes a step for recycling thewater-absorbing resin fine powder after the classification step, beforethe drying step. Recycling of fine powder is capable of contributing toparticle size control or enhancement of water-absorbing speed or liquidpermeability. Recycling amount of fine powder is in a range of 0.1 to40% by weight, still more 1 to 30% by weight, and particularly 5 to 25%by weight, in the pulverized polymer.

A sa recycling method of fine powder, a known method is used, includingrecycling to a monomer (for example, U.S. Pat. No. 5,455,284, U.S. Pat.No. 5,342,899, U.S. Pat. No. 5,264,495, US-A-2007/0225422), recycling topolymer gel (US-A-2008/0306209, U.S. Pat. No. 5,478,879, U.S. Pat. No.5,350,799), recycling to the granulation step (U.S. Pat. No. 6,228,930,U.S. Pat. No. 6,458,921), recycling to a gelling step (U.S. Pat. No.4,950,692, U.S. Pat. No. 4,970,267, U.S. Pat. No. 5,064,582), or thelike, however, among these, recycling to the polymerization step or thedrying step (after granulation or hydration, as needed) is preferable.

(8) Number of Apparatuses at and Subsequent to the Classification Step

In the present invention, from the viewpoint of properties enhancement,the polymerization step is performed by continuous belt polymerizationor continuous kneader polymerization, and as shown in FIG. 12, it ispreferable that a plurality of the pulverization steps and/or theclassification steps, still more the surface processing step areperformed in parallel for the polymerization step. By operating theclassification steps and/or the pulverization steps, in particular, atleast the classification steps, in parallel, properties are enhancedmore, by multiple division of a classification mesh having the samearea, for example, from one sieve with 1 m² to two sieves with 0.5 m²and thus it is preferable. It should be noted that, in FIG. 12, thepulverization apparatuses (c1, c2) are used in combination in series,and the water-absorbing resin is equally divided to two portions afterthe pulverization step c1, and the pulverization step c2 (thepulverization apparatus c2) and the classification step d (theclassification apparatus d) are set as two lines in parallel.

In the production method of the present invention, from the viewpoint ofenhancement and stabilization of properties of the water-absorbingresin, preferably at least one of the pulverization step, theclassification step and the surface cross-linking step is set two ormore lines, relative to one line of the polymerization step. “One line”in the present invention means one line which proceeds via each stepfrom a raw material (a monomer), to obtain polymer gel, thewater-absorbing resin (including a fine powder product recovered), aparticulate water-absorbing agent, and a final product. In the casewhere the line branches to two, it is called “two lines”. In otherwords, “two or more lines” means an embodiment for installing two ormore units of apparatuses in parallel, in the same step, to operate atthe same time or alternatively. Typically, by branching theclassification step to two or more lines, properties can be enhancedmore.

In the present invention, in the case where each step including theclassification step or the like is set in 2 or more lines, the upperlimit for each step is about 10 lines, and among them, preferably 2 to 4lines, still more preferably 2 to 3 lines, and particularly preferably 2lines. By setting the number of line within the above range, propertiesof the obtained water-absorbing resin is enhanced. The case of too manylines (divisions) does not provide effect of division, as well as makesoperation complicated, and not economical from the viewpoint of cost,therefore 2 lines, that is, operation of 2 or more units of the sameapparatuses (particularly 2 units of apparatuses) in parallel at thesame time is particularly preferable.

In addition, in the above embodiment, polymer gel or the water-absorbingresin, which is a dried substance thereof, is divided to 2 or more linesat and subsequent to the drying step, and ratio of the division amountmay be determined by each step, and not especially limited. For example,in the case of two divisions, it is preferably 4:6 to 6:4, morepreferably 4.5:5.5 to 5.5:4.5, still more preferably 4.8:5.2 to 5.2:4.8,and most preferably 5:5. Even in the case of 3 or more lines, it ispreferable that ratio of the maximum amount and the minimum amountdivided to n is within the above range. It should be noted that thedivision operation may be a continuous-type or a batch-type, and ratioof the above division amount is specified by average amount inpredetermined period of time.

In the present invention, number of lines of the surface cross-linkingstep is not especially limited, and an arbitrary number of lines may beselected, however, in considering plant construction cost, running costor the like, it is preferable to be 1 line or 2 lines, in particular, 2lines. That is, from the viewpoint of properties, it is most preferablethat the surface cross-linking step, preferably still more thepulverization step and the classification step are all 2 or more lines(the upper limit is the above range), for 1 line of the polymerizationstep.

In addition, in the case where a plurality of apparatuses are installedin parallel in the present invention, as substitution of 1 apparatus,the apparatuses in parallel may be down sized as appropriate. Even bydown-sizing processing capability of an apparatus to ½, price of theapparatus does not decrease to ½, however, it has been found that in thepresent invention, installment of specific apparatuses in parallelenhances properties of the obtained water-absorbing agent, decreasesratio of out of specification, thus also resulting in cost down.

It should be noted that US-A-2008/0227932 specification has disclosed amethod for performing “polymerization in 2 lines” and the latter half in1 line, US-A-2007/149760 has disclosed a technology for “connecting inseries” a stirring drying apparatus and a heating treatment machine insurface cross-linking, as well as WO 2009/001954 has disclosed atechnology for “connecting in series” a belt polymerization apparatus.On the contrary, in the present invention, properties enhancement andstabilization more than conventional level are attained by “arranging(substantially the same) apparatuses in parallel” in a specific stepafter completion of the polymerization step, relative to 1 unit of apolymerization machine.

(Division Method)

To make surface cross-linking in 2 or more lines, the present inventionincludes a division step, and preferably the division step ofparticulate hydrogel or the particulate water-absorbing resin, which isa dried substance thereof, and more preferably the division step of theparticulate water-absorbing resin.

As the division method to be used, for example, the following methods(a) to (c) are used for the particulate water-absorbing resin afterdrying.

(a) A division method for the particulate water-absorbing resin justafter storing it in a hopper. Preferably, a constant feeder for a powderis used. As the constant feeder, a circle feeder or a screw feeder orthe like is used suitably.(b) A division method for the particulate water-absorbing resin intransporting it to a plurality of hoppers using pneumatictransportation.(c) A division method for the particulate water-absorbing resin infalling (for example, free falling).

In this case, a two-divider or a three-divider installed with a mountainor a weir is used for division. It should be noted that a JIS Rifflesampler (a two-divider) is partitioned to many small rooms and has astructure where the charged sample is allocated alternately in twodirections.

For example, the following methods (d) to (f) or a method in combinationthereof are used for polymer gel after polymerization, and then it issupplied to the drying steps in parallel.

(d) A division method for particulate hydrogel obtained using a kneaderor a meat chopper, in falling (for example, free falling). For thedivision, a two-divider or a three-divider installed with a mountain ora weir and the like is used at the exit of the kneader or the meatchopper.(e) A division method for the particulate hydrogel using the constantfeeder.(f) A cutting method for sheet-like gel obtained by belt polymerization.

Among these, it is preferable that at least the particulatewater-absorbing resin after drying is divided, and to attain this,polymer gel or the particulate dried substance is divided.

It should be noted that preferable value of division ratio of theparticulate water-absorbing resin or polymer gel to be divided in theabove embodiment is as described above.

Among these, from the viewpoint of constant feeding properties, themethods (a) to (c) are preferably used, and the method (a) is still morepreferably used.

(9) Surface Cross-Linking Step (a) Cross-Linking Agent

In the present invention, the surface cross-linking step is furtherincluded after the pulverization step under the above circulationpulverization ratio, and the classification step after drying. Theproduction method of the present invention is applied to the productionmethod for the water-absorbing resin with absorbency against pressure(AAP) and liquid permeability (SFC), or continuous production in a largescale (in particular, 1 [t/hr]), and in particular, to thewater-absorbing resin for surface cross-linking at high temperature. Thesurface cross-linking may be a radical cross-linking by the addition ofa polymerization initiator such as a perfulfate salt or aphotopolymerization initiator, or may be polymerization cross-linkingfor polymerization by the simple addition of a monomer at the surface,or coating cross-linking by the addition of a water-soluble polymer anda cross-linking agent at the surface, however, surface cross-linkingusing a surface cross-linking agent to be described later, which iscapable of reacting with a carboxyl group of polyacrylic acid, ispreferably applied.

In the present invention, a covalent bonded-type surface cross-linkingagent is used, and preferably, the covalent bonded-type surfacecross-linking agent and an ion bonding-type surface cross-linking agentare used in combination.

(Covalent Bonded-Type Surface Cross-Linking Agent)

As the surface cross-linking agent which can be used in the presentinvention, various organic or inorganic cross-linking agents may beexemplified, however, a covalent bonded-type surface cross-linking agent(organic surface cross-linking agent) is preferably used. From theviewpoint of properties, preferably, as the covalent bonded-type surfacecross-linking agent, there can be used a polyhydric alcohol compound, anepoxy compound, a polyvalent amine compound or a condensate thereof witha haloepoxy compound thereof, an oxazoline compound, a (mono-, di-, orpoly-) oxazolidinone compound, and an alkylene carbonate compound; inparticular, a dehydration reactive cross-linking agent, composed of thepolyhydric alcohol compound, the alkylene carbonate compound and theoxazolidinone compound, which requires reaction at high temperature. Inthe case where the dehydration reactive cross-linking agent is not used,compounds which have been exemplified in U.S. Pat. No. 6,228,930, U.S.Pat. No. 6,071,976, U.S. Pat. No. 6,254,990 or the like are morespecifically included. For example, there have been included apolyhydric alcohol compound, such as mono-, di-, tri-, tetrapropyleneglycerin, 1,3-propanediol, glycol, 1,4-butanediol, 1,3-butanediol,1,5-pentanediol, 1,6-hexanediol, sorbitol; an epoxy compound such asethylene glycol diglycidyl ether, glycidol; an alkylene carbonatecompound such as ethylene carbonate; an oxetane compound; a cyclic ureacompound such as 2-imidazolidinone or the like; and the like.

(Ion Bonded-Type Surface Cross-Linking Agent)

In addition, liquid permeability or the like may be enhanced by usingthe ion bonded-type surface cross-linking agent (inorganic cross-linkingagent), instead of or in addition to the covalent bonded-type surfacecross-linking agent (organic cross-linking agent). As the ionbonded-type surface cross-linking agent to be used, there isexemplified, a salt (an organic salt or an inorganic salt) or ahydroxide of a divalent or more, preferably trivalent or tetravalentpolyvalent metal. As the polyvalent metal which can be used, aluminum,zirconium, or the like are included, and as the salt of the polyvalentmetal, aluminum lactate and aluminum sulfate are included. These ionbonded-type surface cross-linking agents may be used at the same time orseparately with the covalent bonded-type surface cross-linking agents.Surface cross-linking using the polyvalent metal has been shown in WO2007/121037, WO2008/09843, WO 2008/09842, U.S. Pat. No. 7,157,141, U.S.Pat. No. 6,605,673, U.S. Pat. No. 6,620,889, US-A-2005/0288182,US-A-2005/0070671, US-A-2007/0106013, and US-A-2006/0073969.

In addition, a polyamine polymer, in particular, the one with a weightaverage molecular weight of about 5000 to 1,000,000 may be used at thesame time or separately, other than the above covalent bonded-typesurface cross-linking agent, to enhance liquid permeability or the like.The polyamine polymer to be used has been exemplified, for example, inU.S. Pat. No. 7,098,284, WO 2006/082188, WO 2006/082189, WO 2006/082197,WO 2006/111402, WO 2006/111403, WO 2006/111404, or the like.

(b) Solvent or the Like

Used amount of the surface cross-linking agent is determined asappropriate in about 0.001 to 10 parts by weight, preferably 0.01 to 5parts by weight, relative to 100 parts by weight of the water-absorbingresin. Preferably, water may be used in combination with the surfacecross-linking agent. Amount of water to be used is in a range of 0.5 to20 parts by weight, and preferably 0.5 to 10 parts by weight, relativeto 100 parts by weight of the water-absorbing resin. Also in the case ofusing an inorganic surface cross-linking agent and an organic surfacecross-linking agent in combination, they are used each in an amount of0.001 to 10 parts by weight, and preferably 0.01 to 5 parts by weight.

In addition, in this case, a hydrophilic organic solvent may be used,and amount thereof is in a range of 0 to 10 parts by weight, andpreferably 0 to 5 parts by weight, relative to 100 parts by weight ofthe water-absorbing resin. In addition, in mixing a solution of across-linking agent to the water-absorbing resin particle, awater-insoluble fine powder or a surfactant may be present together in arange not to inhibit the effect of the present invention, for example,in 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and morepreferably 0 to 1 parts by weight. A surfactant to be used or usedamount thereof has been exemplified in U.S. Pat. No. 7,473,739 or thelike.

(c) Mixing Apparatus

In the present invention, in mixing a surface processing agent,continuous high speed rotating stirring-type mixing machines, and amongthem, continuous high speed rotating stirring-type mixing machines of ahorizontal-type are used suitably. It should be noted that the surfaceprocessing agent means the surface cross-linking agent or an alternativethereof (for example, a radical polymerization initiator such as apersulfate salt, and a monomer), and is a concept including a solutionor a dispersion thereof. Stirring is performed at 100 to 10000 rpm,still more 300 to 2000 rpm, and residence time is preferably within 180seconds, still more 0.1 to 60 seconds, particularly about 1 to 30seconds.

(d) Temperature of the Water-Absorbing Resin

In the present invention, temperature of the water-absorbing resinpowder (the particulate water-absorbing agent) to be supplied to thesurface cross-linking step or a transportation pipeline is preferably30° C. or higher, more preferably 40° C. or higher, and still morepreferably 50° C. or higher. By maintaining the temperature of thewater-absorbing resin powder (particulate water-absorbing agent) to besupplied to the transportation pipeline at predetermined temperature orhigher, decrease in properties of the particulate water-absorbing agentis suppressed. Specifically, it has a significant effect to maintainproperties such as saline flow conductivity (SFC).

(e) Structure of a Heating Apparatus

It should be noted that as such a continuous heating treatment machine,a horizontal-type continuous stirring apparatus or the like, providedwith a charging port, an discharge port of the water-absorbing resin, astirring means composed of one or more rotation axes having a pluralityof stirring blades, and a heating means, is used. In addition, thepresent invention provides a production method for the acrylic acid(salt)-based water-absorbing resin, where, preferably, a cross-linkingreaction is performed under condition of a stirring power index in thiscase of 3 to 15 [W·hr/kg]. In the present description, it is specified:(stirring power index)=((power consumption of an apparatus in surfaceprocessing)−(power consumption in blank operation)×average residencetime)/(processing amount per hour×average residence time), and byadoption of a specific apparatus and a specific parameter (stirringpower index) thereof, the water-absorbing resin with superior propertiescan be obtained continuously and stably, even in scale up to 1 [t/hr] ormore.

Stirring power index may be determined easily from power consumption ofan apparatus in surface processing, and power consumption in blankoperation, and when it is over 15 [W·hr/kg], properties (in particular,liquid permeability) decreases, while also when it is below 3 [W·hr/kg],properties (in particular, absorbency against pressure) decreases.Stirring power index is more preferably in a range of 4 to 13 [W·hr/kg],still more preferably 5 to 11 [W·hr/kg], 5 to 10 [W·hr/kg] andparticularly preferably 5 to 9 [W·hr/kg].

(f) Operation Conditions of the Heating Apparatus

The water-absorbing resin after being added with a surface processingagent in the above mixing apparatus is subjected to heating treatment.An essential apparatus is the horizontal-type continuous stirringapparatus, and the water-absorbing resin after being mixed with thesurface cross-linking agent is subjected to heating treatment, and thencooling treatment as needed. Heating temperature is 70 to 300° C.,preferably 120 to 250° C., and more preferably 150 to 250° C., andheating time is preferably in a range of 1 minute to 2 hours.

Heating treatment may be performed using a usual drying machine or aheating furnace. In the present invention, even in drying with hightemperature heating or air (hot air), which has conventionally causedsignificant coloring, the water-absorbing resin with high whiteness canbe provided. In particular, in the case of aiming at a sanitary material(in particular, the disposable diapers), by such surface cross-linking,it is enough to enhance absorbency against pressure (AAP) up to a rangewhich will be described later, preferably 20 [g/g] or higher, and stillmore about 23 to 30 [g/g].

(g) Cooling Step and the Second Classification Step

The cooling step is a step performed arbitrarily after the surfaceprocessing step, and the cooling step can be used, in the case of usinga dewatering reactive cross-linking agent, which requires a reactionpreferably at high temperature, composed of a polyvalent alcoholcompound, an alkylene carbonate compound, and an oxazolidinone compound.

The cooling apparatus to be used in this cooling step is not especiallylimited, and it may be the above horizontal-type continuous stirringapparatuses to be used in the heating treatment, or a two axes stirringdrying machine, for example, having cooling water passed through theinside of the inner wall and other heat conduction plane, exemplified inU.S. Pat. No. 7,378,453 or the like, may be used. In addition,temperature of this cooling water is set at below the heatingtemperature in the surface processing step, and preferably at 25° C. orhigher and below 80° C.

(10) Other Steps

As other than the above steps, a recycling step of an evaporatedmonomer, a granulation step, and a fine powder removal step, or the likemay be installed, as needed. Still more, to reduce coloring over time orto prevent gel deterioration or the like, the additives to be describedlater may be used in the monomer or a polymer thereof.

[3] Properties of the Water-Absorbing Resin (1) Properties of theWater-Absorbing Resin

In the case of aiming at sanitary materials, in particular, disposablediapers, it is preferable to control by the above polymerization orsurface cross-linking, so as to satisfy at least one of the followingfeatures (a) to (e), still more two or more including AAP, andparticularly preferably three or more including AAP. The case, where thefollowing features are not satisfied, may not exert sufficientperformance in high concentration disposable diapers to be describedlater.

The production method of the present invention is applicable suitably tothe production method of the following water-absorbing resin, andpreferably applicable to control and enhance liquid permeability (SFC)or water-absorbing speed (FSR). It should be noted that, unlessotherwise specified, properties of the following and in Examples arespecified by the EDANA method.

(a) Absorbency Against Pressure (AAP)

To prevent leakage in disposable diapers, using the above polymerizationas an example of an attainment means, it is controlled so as to attainan absorbency (AAP) of preferably 20 [g/g] or higher, more preferably 22[g/g] or higher, still more preferably 24 [g/g] or higher, for the 0.9%by weight sodium chloride aqueous solution, against a pressure of 1.9kPa, still more against a pressure of 4.8 kPa.

(b) Liquid Permeability (SFC)

To prevent leakage in disposable diapers, using the above polymerizationas an example of an attainment means, it is controlled so as to attainflow conductivity of 0.69% by weight sodium chloride aqueous solution(SFC), which is a liquid permeability characteristics against pressure,of 1 [×10⁻⁷·cm³·s·g⁻¹] or higher, preferably 20 [×10⁻⁷·cm³·s·g⁻¹] orhigher, more preferably 50 [×10⁻⁷·cm³·s·g⁻¹] or higher, still morepreferably 70 [×10⁻⁷·cm³·s·g⁻¹] or higher, and particularly preferably100 [×10⁻⁷·cm³·s·g⁻¹] or higher. A measurement method for SFC is wellknown, and has been described, for example, in U.S. Pat. No. 5,562,646.

According to the present invention, because significant enhancementeffect of liquid permeability is exerted, among them, enhancement ofSFC, in particular, enhancement of SFC up to the above range, inparticular, enhancement of SFC up to 20 [×cm³·s·10⁻⁷·g⁻¹] or higher, thepresent method is suitably applicable for the production method for thewater-absorbing resin with such high liquid permeability.

(c) Absorption Capacity without Load (CRC)

Absorption capacity without load (CRC) is controlled so as to attainpreferably 10 [g/g] or higher, more preferably 20 [g/g] or higher, stillmore preferably 25 [g/g] or higher, and particularly preferably 30 [g/g]or higher. The higher CRC is the better, and the upper limit value isnot especially limited, however, from the viewpoint of balance withother properties, it is preferably 50 [g/g] or lower, more preferably 45[g/g] or lower, and still more preferably 40 [g/g] or lower.

(d) Water Soluble Amount (Extractables)

The water soluble amount is preferably 0 to 35% by weight or lower, morepreferably 25% by weight or lower, still more preferably 15% by weightor lower, and particularly preferably 10% by weight or lower.

(e) Residual Monomer Amount

Using the above polymerization as one example of an attainment means,residual monomer amount is shown to be usually 500 ppm or lower,preferably 0 to 400 ppm, more preferably 0 to 300 ppm, and particularlypreferably 0 to 200 ppm relative to 100% by weight of thewater-absorbing resin.

(f) Water-Absorbing Speed (FSR)

Water-absorbing speed (FSR) of 1 g of the water-absorbing resin to 20 gof a normal saline solution is usually 0.05 [g/g/sec] or higher, 0.1[g/g/sec] or higher, usually 0.15 [g/g/sec] or higher, 0.20 [g/g/sec] orhigher, and still more 0.25 [g/g/sec] or higher, (up to 0.50). The upperlimit is enough at 0.1 [g/g/sec]. A measurement method for FSR has beenspecified in WO 2009/016055.

(g) Amount of Increase in Fine Powder Before and after Damage (DamageResistance)

Amount of increase in fine powder before and after damage (amount ofincrease in the substance passed through 150 μm) specified by ameasurement method of Example is preferably 3% by weight or lower, andstill more 1.5% by weight or lower. Such a range provides no problem ofproperties decrease in practical use such as in production of thedisposable diapers or the like.

(2) Other Additives

Still more, in response to use objects, an oxidizing agent, anantioxidant, water, a polyvalent metal compound, water-insolubleinorganic or organic powder such as silica, metal soap or the like,deodorant, an antibacterial agent, polyamine polymer, pulp orthermoplastic fiber or the like may be added to the water-absorbingresin, in an amount of 0 to 3% by weight, preferably 0 to 1% by weightin 100% by weight of the water-absorbing resin.

(3) Intended Use

Applications of the water-absorbing resin of the present invention arenot especially limited, however, it may be preferably used in absorbentarticles such as disposable diapers, sanitary napkins, incontinent pads.In particular, when it is used in high concentration diapers (thoseusing a large quantity of the water-absorbing resin in one sheet of thediaper), wherein odor or coloring or the like derived from raw materialshas conventionally been a problem, in particular, in the case where itis used in the upper layer part of an absorbing body in the absorbentarticle, particularly superior performance is exerted.

Effect of the present invention is exerted, when content of thewater-absorbing resin (core concentration) in the absorbing body,containing arbitrarily other absorbent material (pulp fiber or thelike), in this absorbing articles, is 30 to 100% by weight, preferably40 to 100% by weight, more preferably 50 to 100% by weight, still morepreferably 60 to 100% by weight, particularly preferably 70 to 100% byweight, and most preferably 75 to 95% by weight. For example, when thewater-absorbing resin of the present invention is used in the aboveconcentration, in particular, in the upper layer part of an absorbingbody, due to superior liquid permeability (liquid permeability againstpressure), diffusion properties of absorbent fluid such as urine issuperior, therefore, such absorbent articles can be provided as havingnot only enhanced absorption amount of the whole absorbent article, dueto efficient liquid distribution of absorbent articles such asdisposable diapers, but also maintaining a white state showing goodsanitary feeling of the absorbing body.

EXAMPLES

Explanation will be given below on the present invention in accordancewith Examples, however, the present invention should not be construedlimitedly by Examples. In addition, various properties described inclaims and Examples of the present invention were determined accordingto EDANA methods and the following measurement methods.

<Measurement Methods for Particle Diameter (D50) and LogarithmicStandard Deviation (σζ) of Particle Size Distribution>

Measurement of particle diameter was performed in accordance withmeasurement of weight average particle diameter (D50) described in WO2004/69915.

The water-absorbing resin after pulverization was sieved with standardJIS sieves each having a sieve mesh size of 710 μm, 600 μm, 500 μm, 300μm, 150 μm, and 45 μm, to plot residual percent, R, on logarithmicprobability paper. Each point plotted was connected by a straight line,from which weight average particle diameter (D50) was read.

In addition, logarithmic standard deviation (σζ) is represented by thefollowing equation, provided that X1 is particle diameter at R=84.1% byweight and X2 is particle diameter at R=15.9% by weight, and the smallervalue of σζ means the narrower particle size distribution.

σζ=0.5×ln(X2/X1)

It should be noted that, in the case of containing the water-absorbingresin having particle diameter over 850 μm, a commercial JIS standardsieve having a sieve mesh size over 850 μm is used, as appropriate.

In measurement of particle size and logarithmic standard deviation (σζ)of particle size distribution, 10.0 g of the water-absorbing resinparticle was charged in the JIS standard sieves, each having a sievemesh size of 710 μm, 600 μm, 500 μm, 300 μm, 150 μm, and 45 μm (THE IIDATESTING SIEVE: a diameter of 8 cm), to classify for 5 minutes, using avibration classification apparatus (IIDA SIEVE SHAKER, TYPE: ES-65, SER.No. 0501).

It should be noted that the pulverization step and the classificationstep are performed under reduced pressure, and still more between thepulverization step and the classification step, as well as before andafter these steps are at a temperature of about 60° C. and connected bythe following pneumatic transportation (a dew point of −15° C. and atemperature of about 30° C.). In addition, the water-absorbing resinpowder after surface cross-linking is hereafter called thewater-absorbing agent (particulate water-absorbing agent).

Example 1

A continuous production apparatus of a water-absorbing resin was used,where each apparatus at a polymerization step (stationary polymerizationon a belt), a step for gel crush (crushing), a drying step, apulverization step, a classification step, a surface cross-linking step(a spraying step of a surface cross-linking agent, a heating step), acooling step, a particle size adjusting step, and a transportation stepbetween each step is connected to be able to perform each stepcontinuously. Each step may be one line or two or more lines (branchedin parallel, refer to FIG. 4), and in the case where two or more linesare adopted in the following Examples, production capacity is shown bytotal amount of the whole lines. Production capacity of this continuousproduction apparatus is about 3500 kg/hr. Using this continuousproduction apparatus, the water-absorbing resin powder was producedcontinuously.

Firstly, a monomer aqueous solution (1) consisting of the followingcomposition was prepared.

A monomer aqueous solution (1)

Acrylic acid: 193.3 parts by weight

A 48% by weight aqueous solution of sodium hydroxide: 64.4 parts byweight

Polyethyleneglycol diacrylate (an average n number of 9): 1.26 parts byweight

A 0.1% by weight aqueous solution of penta sodiumethylenediaminetetra(methylenephosphonate): 52 parts by weight

Deionized water: 134 parts by weight

Next, temperature of the monomer aqueous solution (1) was adjusted at40° C. The obtained monomer aqueous solution (1) was continuously fedusing a constant feed pump to perform continuous mixing of 97.1 parts byweight of the 48% by weight aqueous solution of sodium hydroxide intothe monomer aqueous solution (1) using line mixing. Temperature of themonomer increased up to 85° C. by neutralization heat in this time.

Then, 8.05 parts by weight of a 4% by weight aqueous solution of sodiumpersulfate was continuously mixed using line mixing.

A continuously mixed substance obtained by this line mixing was suppliedonto a plane belt having weirs at both ends, in a thickness of about 7.5mm to perform polymerization continuously for 3 minutes to obtain ahydrogel-like cross-linked polymer (1).

This hydrogel-like cross-linked polymer (1) was cut continuously in avertical direction to a travelling direction of the belt, and in nearlythe same interval. Next, it was finely cut to about 1.5 mm using a meatchopper with a pore diameter of 22 mm. This finely cut gel was spreadand put on a continuous transferring porous plate of a through flow banddrying machine, to dry at 185° C. for 30 minutes to obtain 246 parts byweight (total discharge amount of the water-absorbing resin at thedrying step) of a dried polymer (1).

By continuously supplying the whole amount of the dried polymer (1)(about 60° C.) to a three-stage roll mill for pulverization, apulverized polymer (1) was obtained. Roll gaps of this three-stage rollmill were 0.8 m/0.65 mm/0.48 mm from the top side, in this order. Degreeof reduced pressure of the pulverization step was set as 0.29 kPa.

After this pulverization step, the obtained pulverized polymer (1)(about 60° C.) was classified continuously using a sievingclassification apparatus having metal sieving meshes each having a sievemesh size of 710 μm and 175 μm, to obtain particles (A) which did notpass through the sieve of 710 μm, particles (B) passed through the sieveof 710 μm but not passed through the sieve of 175 μm, and particles (C)passed through the sieve of 175 μm. The particles (A) not passed throughthe sieve of 710 μm were supplied again to the three-stage roll mill forpulverization. It should be noted that degree of reduced pressure of theclassification step was set at 0.11 kPa, and air having a dew point of10° C. and a temperature of 75° C. was passed through inside the sievingapparatus in a rate of 2 [m³/hr]. Classification was performed using anoscillation-type circular sieving classification apparatus (number ofvibration: 230 rpm, radial inclination (gradient): 11 mm, tangentialinclination (gradient): 11 mm, amount of eccentricity: 35 mm,temperature of the apparatus: 55° C.), and the stand installed with thissieving classification apparatus was grounded (electricity removal) witha grounding resistance value of 5Ω.

Amount of the particles (A) not passed through the sieve of 710 μm,recycled this time, was 175 parts by weight. That is, total supplyamount to the 3-stage roll mill was 421 parts by weight (total supplyamount of the water-absorbing resin to the pulverization step), andcirculation pulverization ratio was 1.71. In this way, water-absorbingresin powder (1), having a particle diameter of 710 to 175 μm, wasobtained continuously.

After uniformly mixing a surface processing agent (containing thecovalent-bonded-type surface cross-linking agent), as a mixed solutioncomposed of 0.3 part by weight of 1,4-butane diol, 0.6 part by weight ofpropylene glycol and 3.0 parts by weight of deionized water, into 100parts by weight of the obtained water-absorbing resin powder (1), themixture was subjected to heating treatment at 208° C. for 40 minutes.Next, it was cooled and a mixed solution composed of 1.17 parts byweight of a 27.5% by weight of aqueous solution of aluminum sulfate (8%by weight as converted to aluminum oxide) as the ion-bondedcross-linking agent, 0.196 part by weight of a 60% by weight of aqueoussolution of sodium lactate, and 0.029 part by weight of propyleneglycol, was uniformly mixed.

After that, the obtained particles were crushed till passing through theJIS standard sieve with a sieve mesh size of 710 μm. It should be notedthat crushing in this description is an operation to loosen an aggregatein surface cross-linking of the water-absorbing resin powder (1) havinga particle diameter of 710 to 175 μm, as a substance passing through 710μm. In this way, a water-absorbing agent (1) composed of the surfacecross-linked water-absorbing resin powder (1) was obtained.

Example 2

In a similar operation as in the Example 1, the particles (C) whichpassed through the sieve of 175 μm were granulated, in accordance with amethod of “Granulation Example 1” described in the description of U.S.Pat. No. 6,228,930 specification. This granulated substance, togetherwith the gel crushed gel using a meat chopper, was spread and put on atransferring porous plate of a through flow band drying machine, to dryat 185° C. for 30 minutes to obtain 295 parts by weight (total dischargeamount of the water-absorbing resin at the drying step) of a driedpolymer (1).

At and subsequent to the drying step, the same operation as in theExample 1 was performed. In this way, a water-absorbing agent (2)composed of the surface cross-linked water-absorbing resin powder (2)was obtained. It should be noted that amount of the particles (A) whichdid not pass through the sieve of 710 μm, recycled this time, was 172parts by weight. That is, total supply amount to the 3-stage roll millwas 467 parts by weight (total supply amount of the water-absorbingresin to the pulverization step), and circulation pulverization ratiowas 1.58.

Example 3

In a similar operation as in the Example 1, roll mill gap was adjustedarbitrarily so that recycled amount of the particles (A) which did notpass through the sieve of 710 μm, attained 295 parts by weight (recycledamount varies depending on the sieve size or supply amount or the like,however, it is adjustable to arbitrary recycled amount by adjustment ofroll mill clearance. That is, total supply amount to the 3-stage rollmill was 541 parts by weight in this time (total supply amount of thewater-absorbent resin to the pulverization step), and in addition,circulation pulverization ratio was 2.20. In this way, a water-absorbingagent (3) composed of the surface cross-linked water-absorbing resinpowder (3) was obtained.

Comparative Example 1

In a similar operation as in the Example 1, recycling of the particles(A) which did not pass through the sieve of 710 μm, was not performed.That is, total supply amount to the 3-stage roll mill was 246 parts byweight in this time (total supply amount of the water-absorbing resin tothe pulverization step), and in addition, circulation pulverizationratio was 1.00. In this way, a comparative water-absorbing agent (1) wasobtained.

Comparative Example 2

In a similar operation as in the Example 1, roll mill gap was adjustedarbitrarily so that recycled amount of the particles (A) which did notpass through the sieve of 710 μm, attained 17 parts by weight. That is,total supply amount to the 3-stage roll mill was 263 parts by weight inthis time (total supply amount of the water-absorbing resin to thepulverization step), and in addition, circulation pulverization ratiowas 1.07. In this way, a comparative water-absorbing agent (2) wasobtained.

Comparative Example 3

In a similar operation as in the Example 1, roll mill gap was adjustedarbitrarily so that recycled amount of the particles (A) which did notpass through the sieve of 710 μm, attained 65 parts by weight. That is,total supply amount to the 3-stage roll mill was 311 parts by weight inthis time (total supply amount of the water-absorbing resin to thepulverization step), and in addition, circulation pulverization ratiowas 1.26. In this way, a comparative water-absorbing agent (3) wasobtained.

Comparative Example 4

In a similar operation as in the Example 1, roll mill gap was adjustedarbitrarily so that recycled amount of the particles (A) which did notpass through the sieve of 710 μm, attained 120 parts by weight. That is,total supply amount to the 3-stage roll mill was 366 parts by weight inthis time (total supply amount of the water-absorbing resin to thepulverization step), and in addition, circulation pulverization ratiowas 1.49. In this way, a comparative water-absorbing agent (4) wasobtained.

Example 7

A similar operation as in the Example 2 was performed, except that thepulverization system shown in FIG. 11 was used.

In this pulverization system, sieve mesh size of the top stage sieve ofthe first sieve was 15 mm, and particles (A′), which did not passethrough the sieve of 15 mm, were supplied to a pulverization machine(PinMill). Next, there was a sieve with sieve mesh size of 710 μm underthe sieve of 15 mm, and particles (A1) which did not pass through thisnet were supplied to a 3-stage roll mill. Next, there was a sieve withsieve mesh size of 175 μm under the sieve of 710 μm, and particles (B1)which did not pass through this net were supplied to the surfacecross-linking step. Next, particles (C1) passed through the net having asieve mesh size of 175 μm were supplied to the fine powder recyclingstep.

The particles (A1) were pulverized using the three-stage roll mill andthen classified using the second sieve. The second sieve was composed ofnets each having sieve mesh size of 710 μm and 175 μm from the upperstage (a net having sieve mesh size of 710 μm or larger may be presentat the upper stage of the net of 710 μm. When this net is present, asubstance which does not pass through this net is treated as a substancenot-passed through 710 μm), and classification thereof was performedcontinuously to particles (A2) not passed through the sieve of 710 μm,particles (B2) passed through the sieve of 710 μm but did not passedthrough the sieve of 175 μm, and particles (C2) passed through the sievewith sieve mesh size of 175 μm. Among these, the particles (A2) weresupplied to a 2-stage roll mill.

The particles (A2) were pulverized using the two-stage roll mill andthen classified using the third sieve. The third sieve had the samecomposition as the second sieve, and classification was similarlyperformed continuously to particles (A3) which did not pass through thesieve of 710 μm, particles (B3) passed through the sieve of 710 μm butdid not pass through the sieve of 175 μm, and particles (C3) passedthrough the sieve with sieve mesh size of 175 μm. Among these, theparticles (A3) were supplied to a 1-stage roll mill.

The particles (A3) were pulverized using the 1-stage roll mill and thenclassified using the fourth sieve. The fourth sieve had the samecomposition as the third sieve, and classification was similarlyperformed continuously to particles (A4) which did not pass through thesieve of 710 μm, particles (B4) passed through the sieve of 710 μm butdid not pass through the sieve of 175 μm, and particles (C4) passedthrough the sieve with sieve mesh size of 175 μm. Among these, theparticles (A4) were supplied again to a 1-stage roll mill.

Roll gap of the above roll mill (clearance distance between the rolls)was adjusted so that weight ratio of each particle becomes as follows.

In the present Example, a dried polymer obtained by drying together witha granulated substance, similarly as in the Example 2, was 282.7 partsby weight (total supply amount of the water-absorbent resin at thedrying step).

In addition, weight ratio of each particle was as follows: particle (A1)7.9 parts by weight, particle (A1) 262.6 parts by weight, particle (B1)18.4 parts by weight, particle (C1) 1.7 parts by weight, particle (A2)127.9 parts by weight, particle (B2) 116.6 parts by weight, particle(C2) 18.1 parts by weight, particle (A3) 56.3 parts by weight, particle(B3) 61.5 parts by weight, particle (C3) 10.1 parts by weight, particle(A4) 22.5 parts by weight, particle (B4) 49.5 parts by weight, andparticle (C4) 6.8 parts by weight. In addition, total supply amount ofthe water-absorbing resin to the pulverization system was 477.2 parts byweight, and circulation pulverization ratio was 1.69.

At and subsequent to the drying step, the same operation as in theExample 1 was performed. In this way, a water-absorbent agent (7)composed of the surface cross-linked water-absorbent resin powdersubstance (7) was obtained.

As above, measurement results of amount of increase in fine powder afterdamage was given and SFC of Examples 1 to 3, 7, and Comparative Examples1 to 4 are shown in Table 1, and measurement results of particle sizedistribution are shown in Table 2.

TABLE 1 Property after surface cross-linking circulation generationamount pulverization of fine powder after CRC SFC ratio damage [wt %][g/g] [10⁻⁷·cm³·g·s⁻¹] Comparative comparative 1.00 3.9 28 72 Example 1water-absorbing agent (1) Comparative comparative 1.07 3.8 28 75 Example2 water-absorbing agent (2) Comparative comparative 1.26 1.5 28 89Example 3 water-absorbing agent (3) Comparative comparative 1.49 1.4 2891 Example 4 water-absorbing agent (4) Example 2 water-absorbing 1.581.8 28 105 agent (2) Example 7 water-absorbing 1.69 1.7 28 108 agent (7)Example 1 water-absorbing 1.71 1.6 28 110 agent (1) Example 3water-absorbing 2.20 1.7 28 112 agent (3) * [wt %] means % by weight.

TABLE 2 D50 ≧710 μm ≧600 μm ≧500 μm ≧300 μm ≧150 μm <150 μm [μm] σζ [wt%] [wt %] [wt %] [wt %] [wt %] [wt %] Comparative comparative 394 0.390.0 6.3 23.5 42.8 25.8 1.6 Example 1 water-absorbing agent (1)Comparative comparative 387 0.39 0.0 5.8 22.8 42.7 26.9 1.8 Example 2water-absorbing agent (2) Comparative comparative 392 0.39 0.0 6.5 23.242.6 26.1 1.6 Example 3 water-absorbing agent (3) Comparativecomparative 410 0.40 0.1 10.2 23.5 40.6 24.2 1.4 Example 4water-absorbing agent (4) Example 2 water-absorbing 424 0.37 0.1 9.925.9 41.5 21.5 1.1 agent (2) Example 7 water-absorbing 434 0.36 0.0 10.727.0 41.8 19.6 0.9 agent (7) Example 1 water-absorbing 431 0.37 0.1 10.526.8 40.8 20.8 1.0 agent (1) Example 3 water-absorbing 436 0.36 0.1 11.027.1 41.4 19.5 0.9 agent (3) * [wt %] means % by weight.

As shown in Table 1, Examples 1 to 3, 7 show a lower amount of increasein fine powder after damage, as compared with Comparative Examples 1 to2, and also gave superior result in liquid permeability (SFC) ascompared with Comparative Examples 3 to 4. That is, it is understoodthat, by setting circulation pulverization ratio as larger than 1.50,and further larger than 1.50 and not more than 3.00, a water-absorbingagent having strong damage resistance, as well as superior liquidpermeability (SFC) can be obtained. <Amount of Increase in Fine Powderafter Damage>

As for the water-absorbing agent obtained in Examples or the comparativewater-absorbing agent obtained in Comparative Examples, the followingpaint shaker test 1 was performed, and they were classified using theJIS standard sieve with a sieve mesh size of 150 μm to measure amount ofincrease in particles having a particle diameter of 150 μm or smaller,before and after the test.

[Paint Shaker Test]

The paint shaker test (PS-test) is the one for shaking 30 g of thewater-absorbing resin or a water-absorbing agent, by putting, togetherwith 10 g of glass beads with a diameter of 6 mm, into a glass containerwith a diameter of 6 cm and a height 11 cm, and attaching a paint shaker(Product No. 488, manufactured by Toyo Seiki Seisaku-syo, Ltd.), at arate of 800 cycle/minute (CPM), detail of which has been disclosed inJP-A-9-235378.

The paint shaker test 1 and the paint shaker test 2 are defined as theone where shaking period was set at 30 minutes and 10 minutes,respectively. A water-absorbing agent given damage is obtained byremoving glass beads using the JIS standard sieve with a sieve mesh sizeof 2 mm, after shaking.

Examples 4 to 6 and 8, and Comparative Examples 5 to 8

As for each water-absorbing resin powder (a powder before surfacecross-linking processing) obtained in the experiment operation ofExamples 1 to 3, 7 and Comparative Examples 1 to 4, a similarclassification operation was performed as in the measurement of particlesize distribution, and by adjusting the powder of each fractionclassified to attain particle size distribution to be described later,the water-absorbing resin powder having the same particle sizedistribution was prepared.

These water-absorbing resin powder was subjected to surfacecross-linking processing similarly as in the Example 1, to obtainwater-absorbing agents and comparative water-absorbing agentscorresponding to each of Examples and Comparative Examples where onlyparticle size distribution was changed.

Particle size distribution adjusted was as follows:

Not passed through 710 μm 0% by weight Not passed through 600 μm 6.5% byweight Not passed through 500 μm 23.2% by weight Not passed through 300μm 42.6% by weight Not passed through 150 μm 26.1% by weight Below 150μm 1.6% by weight

Measurement values of amount of increase in fine powder after damage wasgiven and CRC/SFC of Examples 4 to 6, 8 and Comparative Examples 5 to 8are shown in Table 3.

TABLE 3 Properties after adjustment of particle size distribution(properties comparison at the same particle size) water-absorbinggeneration resin powder amount fine used in circulation powder afteradjusting particle pulverization damage CRC SFC size distribution ratio[wt %] [g/g] [10⁻⁷ · cm³ · g · s⁻¹] Comparative comparative Comparative1.00 3.8 28 73 Example 5 water-absorbing Example 1 agent (5) Comparativecomparative Comparative 1.07 3.8 28 74 Example 6 water-absorbing Example2 agent (6) Comparative comparative Comparative 1.26 1.9 28 89 Example 7water-absorbing Example 3 agent (7) Comparative comparative Comparative1.49 1.4 28 90 Example 8 water-absorbing Example 4 agent (8) Example 5water-absorbing Example 2 1.58 1.8 28 104 agent (5) Example 8water-absorbing Example 7 1.69 1.7 28 106 agent (8) Example 4water-absorbing Example 1 1.71 1.6 28 107 agent (4) Example 6water-absorbing Example 3 2.20 1.6 28 110 agent (6) * [wt %] means % byweight.

As shown in Table 3, even when compared in the same particle sizedistribution, Examples 4 to 6 show lower amount of increase in finepowder after damage, as compared with Comparative Examples 5 to 6, andalso gave superior result in SFC as compared with Comparative Examples 7to 8. That is, it is understood that, even for those having the sameparticle size distribution, by setting circulation pulverization ratioas larger than 1.50, and still more over 1.50 and not more than 3.00, awater-absorbing agent having strong damage resistance, as well assuperior SFC can be obtained. Liquid permeability (e.g., SFC) isgenerally increased as the particle size becomes larger. However, whenthe particle size is made larger in order to enhance liquidpermeability, water-absorbing rate tends to decrease due to decrease insurface area. That is, there is a tendency for liquid permeability andwater-absorbing rate to be a trade-off, but the present invention solvessuch a problem, i.e., can enhance the liquid permeability (SFC), whilemaintaining the particle size distribution (without making particleslarger).

Example 9

The water-absorbing agent (2) obtained in the Example 2 was packaged bypneumatic transportation in a pipeline (surface roughness; Rz is 200 nm)using compressed air having a dew point of −15° C. and a temperature of35° C. Decreased ratio of SFC by pneumatic transportation was 1.8%.

Example 109

Pneumatic transportation was performed similarly as in the Example 9,except that the dew point was set at 20° C. Decreased ratio of SFC bypneumatic transportation was 4.8%. From Example 9 and Example 10, it isunderstood that the dew point of specific value or lower is preferable.

Example 11

In the Example 2, the pulverization step and subsequent steps were setat two-lines, in accordance with FIG. 12. As a result, classificationefficiency was enhanced and fine powder (a substance passed through 150μm was 1.1% by weight), which is also an inhibition factor of liquidpermeation, decreased by about half. In addition, also in the case wherethe classification step was set at two-lines, classification efficiencywas enhanced and fine powder decreased by about half similarly.

(Summary)

As is clear from comparison of Examples with Comparative Examples, bycontrolling circulation pulverization ratio, liquid permeation (SFC) ordamage resistance enhances.

An enhancement method for water-absorbing speed by PATENT LITERATURES 25to 49, as conventional technology, has not noticed on the pulverizationstep or the classification step, and has not suggested the presentinvention by control of circulation pulverization ratio. In addition,PATENT LITERATURES 1 to 5 or PATENT LITERATURES 50 to 55 have discloseda pulverization method or a classification method for thewater-absorbing resin, and a removal method for the non-dried substance,however, have not disclosed a circulation pulverization ratio of 1.10 orhigher, and have not suggested the problem or the effect of the presentapplication.

INDUSTRIAL APPLICABILITY

The present invention enhances and stabilizes properties of thewater-absorbing resin, for example, liquid permeability or damageresistance.

DESCRIPTION OF REFERENCE NUMERALS

-   c Pulverization step-   c-1, c-2 Pulverization apparatus-   d Classification step (Classification apparatus)

1. A method for producing water-absorbing resin powder, comprisingsequentially: a polymerization step for polymerizing an aqueous solutionof acrylic acid (salt) to obtain a hydrogel-like cross-linked polymer; adrying step for drying the obtained hydrogel-like cross-linked polymerto obtain a dried polymer; a pulverization step for pulverizing theobtained dried polymer with a pulverizing means to obtain a pulverizedpolymer; a classification step for classifying the obtained pulverizedpolymer to obtain a classified polymer; and a surface cross-linking stepfor surface cross-linking the obtained classified polymer; characterizedin that, at least a part of the classified polymer is supplied again tothe same or different pulverization step, before the surfacecross-linking step, wherein circulation pulverization ratio in thepulverization step, represented by the following equation is larger than1.50:(Circulation pulverization ratio)=(total supply amount of thewater-absorbing resin to the pulverization step)/(total discharge amountof the water-absorbing resin at the drying step)  [EXPRESSION 1] wherein(total supply amount of the water-absorbing resin to the pulverizationstep)=(total discharge amount of the water-absorbing resin at the dryingstep)+(amount of the classified polymer supplied again to the same ordifferent pulverization step).
 2. The method according to claim 1,wherein the classified polymer is supplied again to the samepulverization step before the classification step.
 3. The methodaccording to claim 1, wherein the classified polymer is supplied to adifferent classification step via a different pulverization step.
 4. Themethod according to claim 1, wherein the pulverization step is performedunder reduced pressure.
 5. The method according to claim 1, wherein thepulverization means is a roll-type pulverization machine.
 6. The methodaccording to claim 1, wherein the roll-type pulverization machine andanother pulverization machine are used in combination as thepulverization means.
 7. The method according to claim 1, wherein threeor more kinds of sieves with different sieve mesh size are used in theclassification step.
 8. The method according to claim 1, whereinelectricity is removed from the classification step or the pulverizationstep.
 9. The method according to claim 1, wherein at least one of thepulverization step, the classification step and the surfacecross-linking step is two or more lines per one line of thepolymerization step.
 10. The method according to claim 1, wherein thepulverization step, the classification step and at least a part beforeand after these steps are connected by pneumatic transportation andcarrying is performed at a temperature of a dew point of −5° C. orlower.
 11. The method according to claim 1, wherein a covalentbonded-type surface cross-linking agent and an ion bonded-type surfacecross-linking agent are used in combination simultaneously or separatelyin the surface cross-linking step.
 12. The method according to claim 1,wherein water content of the dried polymer is 8% by weight or less. 13.The method according to claim 1, further comprising a step for recyclingwater-absorbing resin fine powder generating in the classification step,to or before the drying step.
 14. The method according to claim 1,wherein the method is carried out as a continuous production with aproduction amount per unit time of 1 [t/hr] or more.
 15. The methodaccording to claim 1, wherein water-absorbing speed (specified by FSR)of the obtained water-absorbing resin powder is 0.25 [g/g/sec] or more.16. The method according to claim 1, wherein liquid permeability(specified by SFC) of the obtained water-absorbing resin powder is 20[×10⁻⁷·cm³·g·s⁻¹] or more.
 17. The method according to claim 1, whereinratio of particles with a particle diameter of 850 to 150 μm is 95% byweight or more, in the classified polymer to be supplied to the surfacecross-linking step.
 18. The method according to claim 1, wherein theclassified polymer is directly supplied to the pulverization step. 19.The method according to claim 1, wherein the polymerization step and thesubsequent steps are connected to provide a continuous step.
 20. Themethod according to claim 1, wherein the pulverization step and theclassification step are performed at a temperature of 40 to 100° C. 21.The method according to claim 1, wherein a plurality of thepulverization steps and a plurality of the classification steps areconnected in series, and non-passed through substance having objectiveparticle size via the classification steps are supplied to a differentpulverization step.
 22. The method according to claim 1, wherein theclassification step is performed with a mesh sieve and the pulverizationstep is performed with a roll-type pulverization machine.